Supported nonmetallocene catalyst, preparation and use thereof

ABSTRACT

This invention relates to a supported nonmetallocene catalyst and preparation thereof. The supported nonmetallocene catalyst can be produced with a simple and feasible process and is characterized by an easily controllable polymerization activity. This invention further relates to use of the supported nonmetallocene catalyst in olefin homopolymerization/copolymerization, which is characterized by a lowered assumption of the co-catalyst as compared with the prior art.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a U.S. national phase application based onPCT/CN2010/001606, filed Oct. 13, 2010, which claims the priority ofChinese Application Nos. 200910210985.X, filed Nov. 13, 2009;200910210990.0, filed Nov. 13, 2009; 200910210987.9, filed Nov. 13,2009; and 200910210991.5, filed Nov. 13, 2009, the contents of all ofwhich are incorporated by reference herein in their entirety.

TECHNICAL FIELD

The present invention relates to a nonmetallocene catalyst.Specifically, this invention relates to a supported nonmetallocenecatalyst, preparation thereof and use thereof in olefinhomopolymerization/copolymerization.

BACKGROUND ART

The nonmetallocene catalyst, also called as the post-metallocenecatalyst, was discovered in middle and late 1990's, whose central atominvolves nearly all of the transition metal elements. The nonmetallocenecatalyst is comparative to, or exceeds, the metallocene catalyst in someaspects of the performance, and has been classified as the fourthgeneration catalyst for olefin polymerization, following the Zieglercatalyst, the Ziegler-Natta catalyst and the metallocene catalyst.Polyolefin products produced with such catalysts exhibit favorableproperties and boast low production cost. The coordination atom of thenonmetallocene catalyst comprises oxygen, nitrogen, sulfur and phosphor,without containing a cyclopentadiene group or a derivative thereof (forexample, an indene group or a fluorene group). The nonmetallocenecatalyst is characterized in that its central atom shows comparativelystrong electrophilicity and has a cis alkyl metal type or a metal halidetype central structure, which facilitates olefin insertion and σ-bondtransfer. Therefore, the central atom is easily subject to alkylation,and therefore facilitates formation of a cationic active center. Thethus formed complex has a restricted geometrical configuration, and isstereoselective, electronegative and chiral adjustable. Further, theformed metal-carbon bond is easy to be polarized, which furtherfacilitates homopolymerization and copolymerization of an olefin. Forthese reasons, it is possible to obtain an olefin polymer having acomparatively high molecular weight, even under a comparatively highpolymerization temperature.

However, it is known that in the olefin polymerization, the homogeneousphase catalyst suffers from such problems as short service life,fouling, high consumption of methyl aluminoxane, and undesirably low orhigh molecular weight in the polymer product, and thus only findslimited use in the solution polymerization process or the high-pressurepolymerization process, which hinders its wider application in industry.

Chinese patent Nos. 01126323.7, 02151294.9 and 02110844.7, andWO03/010207 disclose a catalyst or catalyst system finding a broadapplication in olefin polymerization. However, the catalyst or catalystsystem should be accompanied by a comparatively high amount ofco-catalysts, to achieve an acceptable olefin polymerization activity.Further, the catalyst or catalyst system suffers from such problem asfouling of the reactor during polymerization.

It is normal to support the nonmetallocene catalyst by a certainprocess, so as to improve the performance of the catalyst in thepolymerization and the particle morphology of the polymer products. Thisis reflected by, moderate reduction of the initial activity of thecatalyst, elongation of the serve life of the catalyst, alleviation orelimination of caking or flash reaction during the polymerization,improvement of the polymer morphology, and increase of the apparentdensity of the polymer, thus extending its use to other polymerizationprocesses, for example, the gas phase polymerization or the slurrypolymerization.

Aiming at the catalysts of the Chinese patent Nos. 01126323.7,02151294.9 and 02110844.7, and WO03/010207, Chinese patent applicationLaid-Open Nos. CN1539855A, CN1539856A, CN1789291A, CN1789292A andCN1789290A, and WO2006/063501, and Chinese application patent No.200510119401.x provide several ways to support same catalyst on acarrier so as to obtain a supported nonmetallocene catalyst. However,each of these applications relates to the technology of supporting atransition metal-containing nonmetallocene organic metallic compound(also referred to as a nonmetallocene catalyst) on a treated carrier,which suffers from such problems as low load of the nonmetallocenecatalyst or less strong bonding with the carrier.

Chinese patent application Laid-Open No. CN1539856A discloses a processfor supporting a nonmetallocene catalyst on a composite carrier,comprising the steps of (1) drying or baking a porous carrier (as thecarrier) at 100 to 1000° C., under an inert atmosphere or under areduced pressure for 1 to 24 hours to thermally activate same; (2)dissolving a magnesium compound in a tetrahydrofuran-alcohol mixingsystem to obtain a solution, and then adding the thermally activatedporous carrier to the solution, to sufficiently react with each other at0 to 60° C. under stirring to obtain a transparent system, uponfiltration, washing, drying and suction drying, to obtain a compositecarrier; or introducing into the transparent solution a non-polarorganic solvent to sufficiently precipitate same, and then uponfiltration, washing, drying and suction drying to obtain a compositecarrier; (3) dissolving a nonmetallocene catalyst for olefinpolymerization in a solvent, and then contacting same with the compositecarrier or the modified carrier for 12 to 72 hours, upon filtration,washing, drying and suction drying, to obtain the supportednonmetallocene catalyst. According to this process, it is necessary toprepare the composite carrier at the first place and then contactingsame with the catalyst solution.

Most of the prior art olefin polymerization catalysts are metallocenecatalyst-based, for example, those according to U.S. Pat. No. 4,808,561and U.S. Pat. No. 5,240,894, Chinese patent application Laid-Open Nos.CN1344749A, CN1126480A, CN1307594A, CN1103069A, and CN1363537A, and U.S.Pat. No. 6,444,604, EP 0685494, U.S. Pat. No. 4,871,705 and EP0206794,and Chinese patent No. 94101358.8. Again, all of these applicationsrelate to the technology of supporting a transition metal-containingmetallocene catalyst on a treated carrier.

EP708116 discloses a process comprising contacting gasified ZrCl4 with acarrier at a temperature ranging from 160□ to 450□ to support thereon,then reacting the supported ZrCl4 with the Li-salt of a ligand to obtaina supported metallocene catalyst, which is finally used for olefinpolymerization in combination with a co-catalyst. The process is ratherundesirable for industrial production since the supporting procedureshould be conducted at a high reaction temperature and under a highvacuum.

By using a supported nonmetallocene catalyst comprising silica gel asthe carrier or as a component of the carrier, a polymer product havingdesirable particle morphology and controlled polymer particle sizedistribution can be obtained. However, the thus obtained catalystsuffers from comparatively low polymerization activity. Further, sincethe ash contains silica gel, the polymer thus obtained finds onlyrestricted application in practice.

According to EUROPEAN POLYMER JOURNAL, 2005, 41, 941 to 947, a supportedmetallocene catalyst can be obtained by treating MgCl2(THF)2 with chloroethyl aluminum, and supporting zirconocene dichloride thereon.Specifically, MgCl2 is dissolved in tetrahydrofuran, after precipitatedby hexane and washed, the thus obtained solid is treated by chloro ethylaluminum, and then supported with zirconocene dichloride.

According to Sun's article “Study of an in-situ process for preparingCpTi(dbma)Cl2/MgCl2 type catalyst and its use for catalyzing ethylenepolymerization” (Gaofenzi Xuebao, 2004, (1):138), magnesium chloride (asthe carrier) is prepared by the Grignard reagent process, and at thesame time, CpTi(dbma)Cl2 is added thereto, so as to produce saidCpTi(dbma)Cl2/MgCl2 type catalyst. According to said article, alkylationand supporting of the catalyst is conducted in one single step, andtherefore the number of the steps for preparing the catalyst can besignificantly reduced.

Chinese patent No. ZL200510080210.7 discloses a process for in-situproducing a supported vanadium-based nonmetallocene catalyst for olefinpolymerization and use thereof, which comprises reacting dialkylmagnesium with acyl naphthol or a β-dione to form magnesium acylnaphthol or magnesium β-dione compound, then reacting with a chloride ofvanadium (IV), so as to form the carrier and the active catalyticcomponent simultaneously.

Chinese patent No. 200610026765.8 discloses a single site Zeigler-Nattacatalyst for olefin polymerization. In this catalyst, a coordinationgroup-containing salicylaldehyde or substituted salicylaldehydederivative is used as the electron donor. The catalyst is produced byintroducing a pre-treated carrier (for example, silica), a metalliccompound (for example, TiCl4) and the electron donor into a magnesiumcompound (for example, MgCl2)/tetrahydrofuran solution and thenpost-treating the resultant.

Chinese patent No. 200610026766.2 is similar to this patent, and relatesto an organic compound containing a hetero atom and use thereof forproducing a Zeigler-Natty catalyst.

Chinese patent No. CN200710162676.0 discloses a supported nonmetallocenecatalyst and preparation thereof, wherein a magnesium compoundcontaining a catalytically active metal directly contacts with anonmetallocene ligand by an in-situ supporting process. The magnesiumcompound containing a catalytically active metal has been prepared byintroducing a Group IVB metal compound into a formed magnesium compoundsolid (for example, a magnesium compound solid or a modified magnesiumcompound solid), under which circumstance, it is impossible for thecatalytically active metal and the magnesium compound to conduct asufficient reaction with each other (contacting and reacting with eachother at the molecular level), and for this reason, the resultantmagnesium compound containing the catalytically active metal necessarilypresents as a heterogeneous matter, which is unfavorable for thenonmetallocene ligand added afterward to bring its function into fullplay.

Similarly, Chinese patent No. 200710162667.1 discloses a supportednonmetallocene catalyst and preparation thereof, wherein a magnesiumcompound containing a nonmetallocene ligand directly contacts with acompound containing a catalytically active metal by an in-situsupporting process. The magnesium compound containing a nonmetalloceneligand has been prepared by introducing a solution of the nonmetalloceneligand into a formed magnesium compound solid (for example, a magnesiumcompound solid or a modified magnesium compound solid), under whichcircumstance, it is impossible for the nonmetallocene ligand and themagnesium compound to conduct a sufficient reaction with each other(contacting and reacting with each other at the molecular level), andfor this reason, the resultant magnesium compound containing anonmetallocene ligand necessarily presents as a heterogeneous matter,which is unfavorable for the nonmetallocene ligand to bring its functioninto full play.

International application No. PCT/CN2008/001739 is based on these twoapplications, and suffers from the above-identified problems.

The catalyst prepared using anhydrous magnesium chloride as a carrierexhibits a high catalytic activity in the olefin polymerization, butthis kind of catalyst is very brittle, prone to crush in thepolymerization reactor, resulting in a poor polymer morphology. Thecatalyst supported on silica has an excellent flowability, useful to afluidized-bed gas-phase polymerization, but the silica-supportedmetallocene and nonmetallocene catalyst shows a lowered catalyticactivity. If magnesium chloride could be appropriately combined withsilica, a catalyst with high catalytic activity, controllable granulesize and good abrasion resistance may be obtained.

Chinese application patent No. ZL01131136.3 discloses a process forproducing a supported metallocene catalyst, which comprises mixing acarrier with a Group IVB transition metal halide in a solvent under thenormal pressure, then directly reacting with the cation ion of a ligand,so as to integrate synthesis and supporting of the metallocene catalystin one step. However, according to this process, the transition metaland the ligand is used at a molar ratio of 1:1, and a proton acceptor(for example, butyl lithium) is required. Further, the ligand to be usedis a bridged or non-bridged metallocene ligand containing acyclopentadiene group.

According to Xiao's article “Study on a novel Ni(acac)2/TiCl4/L ligandcomposite catalyst in ethylene polymerization to produce branchedpolyethylene” (Zhongshan Daxue Xuebao: Natural Science Edition, 2003,42(3):28), anhydrous MgCl2, Ni(acac)2 and L are dissolved in a mixedsolvent of tetrahydrofuran and ethanol, then silica gel is added theretounder stirring. Further, a determined amount of TiCl4 is added theretoto react for a predetermined duration. Then, a predetermined amount ofEt2AlCl is added thereto to react for another predetermined duration.Finally, the resultant is dried by suction to obtain a compositecatalyst comprising MgCl2-silica as the carrier and an α-diimine ligandL-modified Ni(acac)2/TiCl4 supported thereon. By using said catalyst inethylene homopolymerization, branched polyethylene can be obtained.Specifically, in case of the ligand L2, branched polyethylene having abranch degree of 4 to 12 branched chains/1000 C can be obtained.

As can be seen from the aforesaid, the prior art supportednonmetallocene catalyst suffers from low olefin polymerization activity.If one tries to increase the activity, he has to significantly increasethe amount of the co-catalyst to be used. Further, the prior artcatalyst contains such carrier as silica gel for supporting, andtherefore the polymer obtained from polymerization contains a relativelyhigher amount of ash, which is unfavorable for use of the polymer inpractice. Further, the magnesium compound supported catalyst ischaracterized by the heterogeneous composition and distribution formedduring its preparation, which is unfavorable for significant improvementof its catalyst activity.

Further, the prior art supported nonmetallocene catalyst suffers fromthe problem that due to the heterogeneous composition and distributionformed during preparation of the catalyst, the performances and particlemorphology of the polymer product are restricted.

Therefore, there still exists a need for a supported nonmetallocenecatalyst, which can be produced in a simple way and in an industrialscale, free of the problems associated with the prior art supportednonmetallocene catalyst.

SUMMARY OF THE INVENTION

Upon in-depth study of the prior art, the present inventors found that asupported nonmetallocene catalyst produced by using a specific processcan solve the problems identified as aforesaid, whereby achieving thisinvention.

According to this invention, the present process for producing asupported nonmetallocene catalyst can be conducted in the absence of anyproton donor or any electron donor (for example, di-ether compoundsconventionally used in this field for this purpose), without the need ofsevere reaction requirements and reaction conditions. For these reasons,the present process is simple and suitable for industrial application.

Specifically, this invention generally relates to the first to fourthembodiments as follows.

The first embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene ligand in the presence of analcohol in a solvent, to obtain a magnesium compound solution; dryingthe magnesium compound solution to obtain a modified carrier; andtreating the modified carrier with a chemical treating agent selectedfrom the group consisting of Group IVB metal compounds to obtain thesupported nonmetallocene catalyst.

The second embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene ligand in the presence of analcohol in a solvent, to obtain a magnesium compound solution;introducing into the magnesium compound solution a precipitating agentto obtain a modified carrier; and treating the modified carrier with achemical treating agent selected from the group consisting of Group IVBmetal compounds to obtain the supported nonmetallocene catalyst.

The third embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene ligand in the presence of analcohol in a solvent, to obtain a magnesium compound solution; mixing aporous carrier or a thermally activated porous carrier with themagnesium compound solution to obtain a slurry; drying the slurry toobtain a composite carrier; and treating the composite carrier with achemical treating agent selected from the group consisting of Group IVBmetal compounds to obtain the supported nonmetallocene catalyst.

The fourth embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene ligand in the presence of analcohol in a solvent, to obtain a magnesium compound solution; mixing aporous carrier or a thermally activated porous carrier with themagnesium compound solution to obtain a slurry; introducing into theslurry a precipitating agent to obtain a composite carrier; and treatingthe composite carrier with a chemical treating agent selected from thegroup consisting of Group IVB metal compounds to obtain the supportednonmetallocene catalyst.

More specifically, this invention relates to the following aspects.

1. A process for producing a supported nonmetallocene catalyst,comprising the steps of: dissolving a magnesium compound and anonmetallocene ligand in the presence of an alcohol in a solvent, toobtain a magnesium compound solution; drying the magnesium compoundsolution, or introducing into the magnesium compound solution aprecipitating agent, to obtain a modified carrier; and treating themodified carrier with a chemical treating agent selected from the groupconsisting of a Group IVB metal compound to obtain the supportednonmetallocene catalyst.

2. A process for producing a supported nonmetallocene catalyst,comprising the steps of: dissolving a magnesium compound and anonmetallocene ligand in the presence of an alcohol in a solvent, toobtain a magnesium compound solution; mixing a porous carrier or athermally activated porous carrier with the magnesium compound solutionto obtain a slurry; drying the slurry, or introducing into the slurry aprecipitating agent, to obtain a composite carrier; and treating thecomposite carrier with a chemical treating agent selected from the groupconsisting of a Group IVB metal compound to obtain the supportednonmetallocene catalyst.

3. The process according to any of the aforesaid aspects, furthercomprising the step of pre-treating the composite carrier or themodified carrier with an assistant chemical treating agent selected fromthe group consisting of an aluminoxane, an alkylaluminum and anycombination thereof before treating the composite carrier or themodified carrier with the chemical treating agent.

4. The process according to any of the aforesaid aspects, wherein theporous carrier is one or more selected from the group consisting ofolefin homopolymers or copolymers, vinyl alcohol homopolymers orcopolymers, cyclodextrins, polyesters or co-polyesters, polyamides orco-polyamides, vinyl chloride homopolymers or copolymers, acrylic esterhomopolymers or copolymers, methacrylic ester homopolymers orcopolymers, styrene homopolymers or copolymers, partly crosslinkedproducts of these homopolymers or copolymers, refractory oxides orrefractory composite oxides of a Group IIA, IIIA, IVA or IVB metal inthe Periodic Table of Elements, clay, molecular sieve, mica,montmorillonite, bentonite and kieselguhr, preferably one or moreselected from the group consisting of partly crosslinked styrenepolymers, silica, alumina, magnesia, silica-alumina, magnesia-alumina,titanium oxide, molecular sieve and montmorillonite, more preferablysilica.

5. The process according to any of the aforesaid aspects, wherein themagnesium compound is one or more selected from the group consisting ofa magnesium halide, an alkoxy magnesium halide, an alkoxy magnesium, analkyl magnesium, an alkyl magnesium halide and an alkyl alkoxymagnesium, preferably one or more selected from the group consisting ofa magnesium halide, more preferably magnesium chloride.

6. The process according to any of the aforesaid aspects, wherein thesolvent is one or more selected from the group consisting of a C₆₋₁₂aromatic hydrocarbon, a halogenated C₆₋₁₂ aromatic hydrocarbon, an esterand an ether, preferably one or more selected from the group consistingof a C₆₋₁₂ aromatic hydrocarbon and tetrahydrofuran, more preferablytetrahydrofuran, and the alcohol is one or more selected from the groupconsisting of an aliphatic alcohol, an aromatic alcohol and an alicyclicalcohol, wherein the alcohol is optionally substituted by a substituentselected from the group consisting of a halogen atom and a C₁₋₆ alkoxygroup, preferably one or more selected from the group consisting of analiphatic alcohol, more preferable one or more selected from the groupconsisting of ethanol and butanol.

7. The process according to any of the aforesaid aspects, wherein thenonmetallocene ligand is one or more selected from the group consistingof the compounds having the following structure,

preferably one or more selected from the group consisting of thefollowing compound (A) and the following compound (B),

more preferably one or more selected from the group consisting of thefollowing compound (A-1), the following compound (A-2), the followingcompound (A-3), the following compound (A-4), the following compound(B-1), the following compound (B-2), the following compound (B-3), andthe following compound (B-4),

in all of the aforesaid formulae,

q is 0 or 1;

d is 0 or 1;

A is selected from the group consisting of an oxygen atom, a sulfuratom, a selenium atom,

—NR²³R²⁴, —N(O)R²⁵R²⁶,

—PR²⁸R²⁹, —P(O)R³⁰OR³¹, a sulfone group, a sulfoxide group and—Se(O)R³⁹, wherein N, O, S, Se and P each represents a coordinationatom;

B is selected from the group consisting of a nitrogen atom, anitrogen-containing group, a phosphor-containing group and a C₁-C₃₀hydrocarbyl;

D is selected from the group consisting of a nitrogen atom, an oxygenatom, a sulfur atom, a selenium atom, a phosphor atom, anitrogen-containing group, a phosphor-containing group, a C₁-C₃₀hydrocarbyl, a sulfone group, a sulfoxide group,

—N(O)R²⁵R²⁶,

and —P(O)R³²(OR³³), wherein N, O, S, Se and P each represents acoordination atom;

E is selected from the group consisting of a nitrogen-containing group,an oxygen-containing group, a sulfur-containing group, aselenium-containing group, a phosphor-containing group and a cyanogroup, wherein N, O, S, Se and P each represents a coordination atom;

F is selected from the group consisting of a nitrogen atom, anitrogen-containing group, an oxygen-containing group, asulfur-containing group, a selenium-containing group and aphosphor-containing group, wherein N, O, S, Se and P each represents acoordination atom;

G is selected from the group consisting of a C₁-C₃₀ hydrocarbyl, asubstituted C₁-C₃₀ hydrocarbyl and an inert functional group;

Y is selected from the group consisting of a nitrogen-containing group,an oxygen-containing group, a sulfur-containing group, aselenium-containing group and a phosphor-containing group, wherein N, O,S, Se and P each represents a coordination atom;

Z is selected from the group consisting of a nitrogen-containing group,an oxygen-containing group, a sulfur-containing group, aselenium-containing group, a phosphor-containing group and a cyanogroup, wherein N, O, S, Se and P each represents a coordination atom;

→ represents a single bond or a double bond;

— represents a covalent bond or an ionic bond;

R¹ to R⁴, R⁶ to R³⁶, R³⁸ and R³⁹ are each independently selected fromthe group consisting of a hydrogen atom, a C₁-C₃₀ hydrocarbyl, asubstituted C₁-C₃₀ hydrocarbyl and an inert functional group, whereinthese groups may be identical to or different from one another, and anyadjacent groups may form a bond or a ring (preferably an aromatic ring)with one another; and

R⁵ is selected from the group consisting of the lone pair electron onthe nitrogen atom, a hydrogen atom, a C₁-C₃₀ hydrocarbyl, a substitutedC₁-C₃₀ hydrocarbyl, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a selenium-containing group, and aphosphor-containing group, with the proviso that when R⁵ is theoxygen-containing group, the sulfur-containing group, thenitrogen-containing group, the selenium-containing group or thephosphor-containing group, N, O, S, P and Se in the group R⁵ each canact as a coordination atom to coordinate with the central metal atom(the Group IVB metal atom),

more preferably one or more selected from the group consisting of thefollowing compounds,

more preferably one or more selected from the group consisting of thefollowing compounds,

8. The process according to any of the aforesaid aspects, wherein,

the halogen atom is selected from the group consisting of F, Cl, Br andI,

the nitrogen-containing group is selected from the group consisting of

—NR²³R²⁴, -T-NR²³R²⁴ and —N(O)R²⁵R²⁶,

the phosphor-containing group is selected from the group consisting of

—PR²⁸R²⁹, —P(O)R³⁰R³¹ and —P(O)R³²(OR³³),

the oxygen-containing group is selected from the group consisting ofhydroxy, —OR³⁴ and -T-OR³⁴,

the sulfur-containing group is selected from the group consisting of—SR³⁵, -T-SR³⁵, —S(O)R³⁶ and -T-SO₂R³⁷,

the selenium-containing group is selected from the group consisting of—SeR³⁸, -T-SeR³⁸, —Se(O)R³⁹ and -T-Se(O)R³⁹,

the group T is selected from the group consisting of a C₁-C₃₀hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl and an inert functionalgroup,

R³⁷ is selected from the group consisting of a hydrogen atom, a C₁-C₃₀hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl and an inert functionalgroup,

the C₁-C₃₀ hydrocarbyl is selected from the group consisting of a C₁-C₃₀alkyl group, a C₇-C₅₀ alkylaryl group, a C₇-C₅₀ aralkyl group, a C₃-C₃₀cyclic alkyl group, a C₂-C₃₀ alkenyl group, a C₂-C₃₀ alkynyl group, aC₆-C₃₀ aryl group, a C₈-C₃₀ fused-ring group and a C₄-C₃₀ heterocyclegroup, wherein the heterocycle group contains 1 to 3 hetero atom(s)selected from the group consisting of a nitrogen atom, an oxygen atomand a sulfur atom,

the substituted C₁-C₃₀ hydrocarbyl is selected from the group consistingof the C₁-C₃₀ hydrocarbyl having one or more substituent(s) selectedfrom the halogen atom and the C₁-C₃₀ alkyl group,

the inert functional group is selected from the group consisting of thehalogen atom, the oxygen-containing group, the nitrogen-containinggroup, a silicon-containing group, a germanium-containing group, thesulfur-containing group, a tin-containing group, a C₁-C₁₀ ester groupand a nitro group,

the silicon-containing group is selected from the group consisting of—SiR⁴²R⁴³R⁴⁴, and -T-SiR⁴⁵,

the germanium-containing group is selected from the group consisting of—GeR⁴⁶R⁴⁷R⁴⁸, and -T-GeR⁴⁹,

the tin-containing group is selected from the group consisting of—SnR⁵⁰R⁶¹R⁶², -T-SnR⁵³ and -T-Sn(O)R⁵⁴,

R⁴² to R⁵⁴ are each independently selected from the group consisting ofa hydrogen atom, the C₁-C₃₀ hydrocarbyl, the substituted C₁-C₃₀hydrocarbyl and the inert functional group, wherein these groups may beidentical to or different from one another, and any adjacent groups mayform a bond or a ring with one another, and

the group T is defined as aforesaid.

9. The process according to any of the aforesaid aspects, wherein ratioby molar of the magnesium compound (based on Mg) to the nonmetalloceneligand is 1:0.0001-1, preferably 1:0.0002-0.4, more preferably1:0.0008-0.2, more preferably 1:0.001-0.1, ratio of the magnesiumcompound to the solvent is 1 mol:75˜400 ml, preferably 1 mol:150˜300 ml,more preferably 1 mol:200˜250 ml, ratio by molar of the magnesiumcompound (based on Mg) to the alcohol is 1:0.02˜4.00, preferably1:0.05˜3.00, more preferably 1:0.10˜2.50, ratio by weight of themagnesium compound (on a solid basis) to the porous carrier is 1:0.1-20,preferably 1:0.5-10, more preferably 1:1-5, ratio by volume of theprecipitating agent to the solvent is 1:0.2˜5, preferably 1:0.5˜2, morepreferably 1:0.8˜1.5, and ratio by molar of the magnesium compound(based on Mg) to the chemical treating agent (based on the Group IVBmetal) is 1:0.01-1, preferably 1:0.01-0.50, more preferably 1:0.10-0.30.

10. The process according to any of the aforesaid aspects, wherein theprecipitating agent is one or more selected from the group consisting ofan alkane, a cyclic alkane, a halogenated alkane and a halogenatedcyclic alkane, preferably one or more selected from the group consistingof pentane, hexane, heptane, octane, nonane, decane, cyclohexane,cyclopentane, cycloheptane, cyclodecane, cyclononane, dichloromethane,dichloro hexane, dichloro heptane, trichloro methane, trichloro ethane,trichloro butane, dibromo methane, dibromo ethane, dibromo heptane,tribromo methane, tribromo ethane, tribromo butane, chlorinatedcyclopentane, chlorinated cyclohexane, chlorinated cycloheptane,chlorinated cyclooctane, chlorinated cyclononane, chlorinatedcyclodecane, brominated cyclopentane, brominated cyclohexane, brominatedcycloheptane, brominated cyclooctane, brominated cyclononane andbrominated cyclodecane, more preferably one or more selected from thegroup consisting of hexane, heptane, decane and cyclohexane, mostpreferably hexane.

11. The process according to any of the aforesaid aspects, wherein theGroup IVB metal compound is one or more selected from the groupconsisting of a Group IVB metal halide, a Group IVB metal alkylate, aGroup IVB metal alkoxylate, a Group IVB metal alkyl halide, and a GroupIVB metal alkoxy halide, preferably one or more selected from the groupconsisting of a Group IVB metal halide, more preferably one or moreselected from the group consisting of TiCl₄, TiBr₄, ZrCl₄, ZrBr₄, HfCl₄and HfBr₄, more preferably one or more selected from the groupconsisting of TiCl₄ and ZrCl₄.

12. The process according to any of the aforesaid aspects, wherein thealuminoxane is one or more selected from the group consisting of methylaluminoxane, ethyl aluminoxane, isobutyl aluminoxane and n-butylaluminoxane, preferably one or more selected from the group consistingof methyl aluminoxane and isobutyl aluminoxane, and the alkylaluminum isone or more selected from the group consisting of trimethyl aluminum,triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, tri-n-butylaluminum, triisoamyl aluminum, tri-n-amyl aluminum, trihexyl aluminum,tri-iso-hexyl aluminum, diethyl methyl aluminum and ethyl dimethylaluminum, more preferably one or more selected from the group consistingof trimethyl aluminum, triethyl aluminum, tripropyl aluminum andtriisobutyl aluminum, most preferably one or more selected from thegroup consisting of triethyl aluminum and triisobutyl aluminum.

13. The process according to any of the aforesaid aspects, wherein ratioby molar of the magnesium compound (based on Mg) to the assistantchemical treating agent (based on Al) is 1:0-1.0, preferably 1:0-0.5,more preferably 1:0.1-0.5.

14. A supported nonmetallocene catalyst, produced in line with theprocess according to any of the aspects 1 to 13.

15. An olefin homopolymerization/copolymerization process, wherein thesupported nonmetallocene catalyst according to the aspect 14 is used asthe main catalyst, in combination of one or more selected from the groupconsisting of an aluminoxane, an alkylaluminum, a halogenated alkylaluminum, a fluoroborane, an alkylboron and an alkylboron ammonium saltas the co-catalyst, for homopolymerization or copolymerization of theolefin.

16. An olefin homopolymerization/copolymerization process, comprisingthe steps of: producing a supported nonmetallocene catalyst in line withthe process according to any of the aspects 1 to 13; and using thesupported nonmetallocene catalyst as the main catalyst, in combinationof one or more selected from the group consisting of an aluminoxane, analkylaluminum, a halogenated alkyl aluminum, a fluoroborane, analkylboron and an alkylboron ammonium salt as the co-catalyst, forhomopolymerization or copolymerization of the olefin.

Effect of the Invention

According to the first and fourth embodiments of this invention, thefollowing effects can be obtained.

The in-situ process for producing the supported nonmetallocene catalystaccording to this invention is simple and feasible. The nonmetalloceneligand uniformly distributes throughout the magnesium compound or thecomposite carrier. It is easy to adjust the load of the nonmetalloceneligand. By increasing or reducing the ratio by molar of thenonmetallocene ligand to the magnesium compound, it is possible toincrease or decrease the activity for ethylene polymerization of thecatalyst and the content of the comonomer in the polymer, and somewhatbroaden or narrow the molecular weight distribution of the resultantpolymer. Further, it is possible to adjust the viscosity averagedmolecular weight of the ultra high molecular weight polyethylene byaltering the amount of the nonmetallocene ligand to be introduced.

The supported nonmetallocene catalyst produced in line with the processaccording to this invention shows a significant comonomer effect, i.e.the activity in copolymerization is higher than that inhomopolymerization. Further, by the copolymerization, the bulk densityof the polymer can be increased, i.e. the polymer morphology can beimproved, while using MAO as the co-catalyst will enhance the comonomereffect.

According to the process of this invention (concerning the secondembodiment), the magnesium compound solution is sufficientlyprecipitated in the presence of a precipitating agent and then filtered,washed and dried, and therefore the bonding between the essentialmaterials in the catalyst is relatively strong, whereby increasing thepolymer bulk density.

According to the process of this invention (concerning the thirdembodiment), the composite carrier has been produced by directly dryingthe slurry, and therefore it is easy to adjust the composition andamount of the essential materials in the catalyst, and the resultantcatalyst shows increased activity over that obtained by filtering andwashing the slurry.

According to the process of this invention (concerning the fourthembodiment), the slurry is sufficiently precipitated in the presence ofa precipitating agent and then filtered, washed and dried, and thereforethe bonding between the essential materials in the catalyst isrelatively strong, whereby increasing the polymer bulk density.

According to this invention, the supported nonmetallocene catalystobtained by a process wherein the composite carrier or the modifiedcarrier is firstly subject to the treatment with an assistant chemicaltreating agent and then to that with a chemical treating agent showsincreased catalyst activity and polymer bulk density, somewhat increasedcomonomer content, narrowed polymer molecular weight distribution, andincreased viscosity averaged molecular weight for the ultra highmolecular weight polyethylene, as compared with the supportednonmetallocene catalyst obtained by a process wherein the compositecarrier or the modified carrier is subject only to the treatment with achemical treating agent.

Further, the supported nonmetallocene catalyst produced in line withthis invention exhibits significantly high activity in polymerization ofethylene or ethylene with other alpha-olefins.

Still further, the supported nonmetallocene catalyst produced in linewith this invention can be used to obtain an ultra high molecular weightpolyethylene having a relatively higher molecular weight through ahomopolymerization process in the absence of hydrogen gas.

DETAILED DESCRIPTION OF THE INVENTION

This invention will be described in details hereinafter with referenceto the following specific embodiments. However, it is known that theprotection scope of this invention should not be construed as limited tothese specific embodiments, but rather determined by the attachedclaims.

According to this invention, generally disclosed are the following firstto fourth embodiments.

The first embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene ligand in the presence of analcohol in a solvent, to obtain a magnesium compound solution; dryingthe magnesium compound solution to obtain a modified carrier; andtreating the modified carrier with a chemical treating agent selectedfrom the group consisting of Group IVB metal compounds to obtain thesupported nonmetallocene catalyst.

The second embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene ligand in the presence of analcohol in a solvent, to obtain a magnesium compound solution;introducing into the magnesium compound solution a precipitating agentto obtain a modified carrier; and treating the modified carrier with achemical treating agent selected from the group consisting of Group IVBmetal compounds to obtain the supported nonmetallocene catalyst.

The third embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene ligand in the presence of analcohol in a solvent, to obtain a magnesium compound solution; mixing aporous carrier or a thermally activated porous carrier with themagnesium compound solution to obtain a slurry; drying the slurry toobtain a composite carrier; and treating the composite carrier with achemical treating agent selected from the group consisting of Group IVBmetal compounds to obtain the supported nonmetallocene catalyst.

The fourth embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene ligand in the presence of analcohol in a solvent, to obtain a magnesium compound solution; mixing aporous carrier or a thermally activated porous carrier with themagnesium compound solution to obtain a slurry; introducing into theslurry a precipitating agent to obtain a composite carrier; and treatingthe composite carrier with a chemical treating agent selected from thegroup consisting of Group IVB metal compounds to obtain the supportednonmetallocene catalyst.

First of all, the step of obtaining the magnesium compound solutionaccording to the first to fourth embodiments of this invention isdetailedly described as follows.

Specifically, the magnesium compound and the nonmetallocene ligand aredissolved in the presence of an alcohol in a suitable solvent(hereinafter referred to as a solvent for dissolving the magnesiumcompound) to obtain the magnesium compound solution.

As the solvent, a C₆₋₁₂ aromatic hydrocarbon, a halogenated C₆₋₁₂aromatic hydrocarbon, an ester and an ether can be exemplified.Specifically, toluene, xylene, trimethyl benzene, ethyl benzene, diethylbenzene, chlorinated toluene, chlorinated ethyl benzene, brominatedtoluene, brominated ethyl benzene, ethyl acetate and tetrahydrofuran canbe exemplified. Preference is given to the C₆₋₁₂ aromatic hydrocarbon ortetrahydrofuran, more preferably tetrahydrofuran.

The solvents could be used with one kind or as a mixture of two or morekinds at any ratio therebetween.

According to this invention, the term “alcohol” is explained in a normalsense as known in this field, and refers to a C₁₋₁₀ monobasic alcohol.

As the alcohol, exemplified is an aliphatic alcohol, an aromatic alcoholand an alicyclic alcohol, preferably the aliphatic alcohol, morepreferable ethanol and butanol. Further, the alcohol is optionallysubstituted by a substituent selected from the group consisting of ahalogen atom and an alkoxy group.

For example, the aliphatic alcohol could be selected from the groupconsisting of methanol, ethanol, propanol, 2-propanol, butanol,pentanol, 2-methyl pentanol, 2-ethyl pentanol, 2-hexyl butanol, hexanol,2-ethyl hexanol and the like, preferably ethanol, butanol and 2-ethylhexanol.

The aromatic alcohol could be selected from the group consisting ofbenzyl alcohol, benzene ethanol and methyl benzyl alcohol and the like,preferably phenyl ethanol.

The alicyclic alcohol could be selected from the group consisting ofcyclohexanol, cyclopentanol, cyclooctanol, methyl cyclopentanol, ethylcyclopentanol, propyl cyclopentanol, methyl cyclohexanol, ethylcyclohexanol, propyl cyclohexanol, methyl cyclooctanol, ethylcyclooctanol and propyl cyclooctanol and the like, preferablycyclohexanol and methyl cyclohexanol.

The alcohol substituted by the halogen atom could be for example,trichloro methanol, trichloro ethanol and trichloro hexanol and thelike, preferably trichloro methanol.

The alcohol substituted by the alkoxy group could be for example,ethylene glycol ethyl ether, ethylene glycol n-butyl ether and1-butoxy-2-propanol and the like, preferably ethylene glycol ethylether.

The alcohols could be used with one kind or as a mixture of two or morekinds. If more than one alcohols are used as a mixture, the ratio of onealcohol to another alcohol in the mixture could be arbitrarilydetermined, without any limitation thereto.

For preparation of the magnesium compound solution, it is possible tometer the magnesium compound and the nonmetallocene ligand into amixture solvent consisting of the solvent and the alcohol, and dissolvesame therein, or meter the magnesium compound and the nonmetalloceneligand into the solvent, and at the same time or thereafter, to add thealcohol, and dissolve same therein, without any limitation thereto.

During preparation of the magnesium compound solution, it is desirablethat the ratio by molar of the magnesium compound (based on Mg and on asolid basis) to the alcohol is 1:0.02˜4.00, preferably 1:0.05˜3.00, morepreferably 1:0.10˜2.50, while the ratio of the magnesium compound (basedon Mg and on a solid basis) to the solvent for dissolving the magnesiumcompound is generally 1 mol:75˜400 ml, preferably 1 mol:150˜300 ml, morepreferably 1 mol:200˜250 ml.

According to this invention, as the amount of the nonmetallocene ligandto be used, it is desirable that the ratio by molar of the magnesiumcompound (based on Mg and on a solid basis) to the nonmetallocene ligandis 1:0.0001-1, preferably 1:0.0002-0.4, more preferably 1:0.0008-0.2,more preferably 1:0.001-0.1.

The duration for preparing the magnesium compound solution (i.e. theduration for dissolving the magnesium compound and the nonmetalloceneligand) is not specifically limited, usually 0.5 to 24 hours, preferably4 to 24 hours. During preparation of the magnesium compound solution,any stirring means for example, a stirring paddle (whose rotationalspeed could be 10 to 1000 r/min), could be used to facilitatedissolution of the magnesium compound and the nonmetallocene ligand. Ifneeded, heat can be suitably applied to facilitate the dissolution.

The magnesium compound is further described as follows.

According to this invention, the term “magnesium compound” is explainedin a normal sense as known in this field, and refers to an organic orinorganic solid anhydrous Mg-containing compound conventionally used asa carrier for a supported catalyst for olefin polymerization.

According to this invention, as the magnesium compound, a magnesiumhalide, an alkoxy magnesium halide, an alkoxy magnesium, an alkylmagnesium, an alkyl magnesium halide and an alkyl alkoxy magnesium canbe exemplified.

Specifically, the magnesium halide for example, could be selected fromthe group consisting of magnesium chloride (MgCl₂), magnesium bromide(MgBr₂), magnesium iodide (MgI₂) and magnesium fluoride (MgF₂), etc.,such as magnesium chloride.

The alkoxy magnesium halide for example, could be selected from thegroup consisting of methoxy magnesium chloride (Mg(OCH₃)Cl), ethoxymagnesium chloride (Mg(OC₂H₅)Cl), propoxy magnesium chloride(Mg(OC₃H₇)Cl), n-butoxy magnesium chloride (Mg(OC₄H₉)Cl), isobutoxymagnesium chloride (Mg(i-OC₄H₉)Cl), methoxy magnesium bromide(Mg(OCH₃)Br), ethoxy magnesium bromide (Mg(OC₂H₅)Br), propoxy magnesiumbromide (Mg(OC₃H₇)Br), n-butoxy magnesium bromide (Mg(OC₄H₉)Br),isobutoxy magnesium bromide (Mg(i-OC₄H₉)Br), methoxy magnesium iodide(Mg(OCH₃)I), ethoxy magnesium iodide (Mg(OC₂H₅)I), propoxy magnesiumiodide (Mg(OC₃H₇)I), n-butoxy magnesium iodide (Mg(OC₄H₉)I) andisobutoxy magnesium iodide (Mg(i-OC₄H₉)I), etc., such as methoxymagnesium chloride, ethoxy magnesium chloride and isobutoxy magnesiumchloride.

The alkoxy magnesium for example, could be selected from the groupconsisting of methoxy magnesium (Mg(OCH₃)₂), ethoxy magnesium(Mg(OC₂H₅)₂), propoxy magnesium (Mg(OC₃H₇)₂), butoxy magnesium(Mg(OC₄H₉)₂), isobutoxy magnesium (Mg(i-OC₄H₉)₂) and 2-ethyl hexyloxymagnesium (Mg(OCH₂CH(C₂H₅)C₄H)₂), etc., such as ethoxy magnesium andisobutoxy magnesium.

The alkyl magnesium for example, could be selected from the groupconsisting of methyl magnesium (Mg(CH₃)₂), ethyl magnesium (Mg(C₂H₅)₂),propyl magnesium (Mg(C₃H₇)₂), n-butyl magnesium (Mg(C₄H₉)₂) and isobutylmagnesium (Mg(i-C₄H₉)₂), etc., such as ethyl magnesium and n-butylmagnesium.

The alkyl magnesium halide for example, could be selected from the groupconsisting of methyl magnesium chloride (Mg(CH₃)Cl), ethyl magnesiumchloride (Mg(C₂H₅)Cl), propyl magnesium chloride (Mg(C₃H₇)Cl), n-butylmagnesium chloride (Mg(C₄H₉)Cl), isobutyl magnesium chloride(Mg(i-C₄H₉)Cl), methyl magnesium bromide (Mg(CH₃)Br), ethyl magnesiumbromide (Mg(C₂H₅)Br), propyl magnesium bromide (Mg(C₃H₇)Br), n-butylmagnesium bromide (Mg(C₄H₉)Br), isobutyl magnesium bromide(Mg(i-C₄H₉)Br), methyl magnesium iodide (Mg(CH₃)I), ethyl magnesiumiodide (Mg(C₂H₅)I), propyl magnesium iodide (Mg(C₃H₇)I), n-butylmagnesium iodide (Mg(C₄H₉)I) and isobutyl magnesium iodide(Mg(i-C₄H₉)I), etc., such as methyl magnesium chloride, ethyl magnesiumchloride and isobutyl magnesium chloride.

The alkyl alkoxy magnesium for example, could be selected from the groupconsisting of methyl methoxy magnesium (Mg(OCH₃)(CH₃)), methyl ethoxymagnesium (Mg(OC₂H₅)(CH₃)), methyl propoxy magnesium (Mg(OC₃H₇)(CH₃)),methyl n-butoxy magnesium (Mg(OC₄H₉)(CH₃)), methyl isobutoxy magnesium(Mg(i—OC₄H₉)(CH₃)), ethyl methoxy magnesium (Mg(OCH₃)(C₂H₅)), ethylethoxy magnesium (Mg(OC₂H₅)(C₂H₅)), ethyl propoxy magnesium(Mg(OC₃H₇)(C₂H₅)), ethyl n-butoxy magnesium (Mg(OC₄H₉)(C₂H₅)), ethylisobutoxy magnesium (Mg(i-OC₄H₉)(C₂H₅)), propyl methoxy magnesium(Mg(OCH₃)(C₃H₇)), propyl ethoxy magnesium (Mg(OC₂H₅)(C₃H₇)), propylpropoxy magnesium (Mg(OC₃H₇)(C₃H₇)), propyl n-butoxy magnesium(Mg(OC₄H₉)(C₃H₇)), propyl isobutoxy magnesium (Mg(i—OC₄H₉)(C₃H₇)),n-butyl methoxy magnesium (Mg(OCH₃)(C₄H₉)), n-butyl ethoxy magnesium(Mg(OC₂H₅)(C₄H₉)), n-butyl propoxy magnesium (Mg(OC₃H₇)(C₄H₉)), n-butyln-butoxy magnesium (Mg(OC₄H₉)(C₄H₉)), n-butyl isobutoxy magnesium(Mg(i-OC₄H₉)(C₄H₉)), isobutyl methoxy magnesium (Mg(OCH₃)(i-C₄H₉)),isobutyl ethoxy magnesium (Mg(OC₂H₅) (i-C₄H₉)), isobutyl propoxymagnesium (Mg(OC₃H₇) (i-C₄H₉)), isobutyl n-butoxy magnesium (Mg(OC₄H₉)(i-C₄H₉)) and isobutyl isobutoxy magnesium (Mg(i-OC₄H₉) (i-C₄H₉)), etc.,such as butyl ethoxy magnesium.

The magnesium compounds could be used with one kind or as a mixture oftwo or more kinds, but without any limitation thereto.

For example, if more than one magnesium compounds are used as a mixture,the ratio by molar of one magnesium compound to another magnesiumcompound in the mixture could be, for example, 0.25 to 4:1, such as 0.5to 3:1, such as 1 to 2:1.

According to this invention, the term “nonmetallocene complex” refers toan organic metallic compound capable of exhibiting a catalysis activityin olefin polymerization when combined with an aluminoxane (sometimeshereinafter referred to as a nonmetallocene complex for olefinpolymerization). The compound contains a central metal atom and at leastone multi-dentate ligand (preferably a tri or more-dentate ligand)bonding to the central metal atom by a coordination bond. The term“nonmetallocene ligand” corresponds to the multi-dentate ligand.

According to this invention, the nonmetallocene ligand is selected fromthe compounds having the following structure,

According to this invention, the groups A, D and E (the coordinationgroups) in the compound form a coordination bond by a coordinationreaction with the Group IVB metal atom contained in the Group IVB metalcompound used as the chemical treating agent herein through thecoordination atoms (for example, hetero atoms like N, O, S, Se and P)contained in these groups, whereby forming a complex (i.e. thenonmetallocene complex according to this invention) having said GroupIVB metal atom as the central atom.

According to a further embodiment of this invention, the nonmetalloceneligand is selected from the following compound (A) and the followingcompound (B),

According to a further embodiment of this invention, the nonmetalloceneligand is selected from the following compound (A-1), the followingcompound (A-2), the following compound (A-3), the following compound(A-4), the following compound (B-1), the following compound (B-2), thefollowing compound (B-3), and the following compound (B-4),

In all of the aforesaid formulae,

q is 0 or 1;

d is 0 or 1;

A is selected from the group consisting of an oxygen atom, a sulfuratom, a selenium atom,

—NR²³R²⁴, —N(O)R²⁵R²⁶,

—PR²⁸R²⁹, —P(O)R³⁰OR³¹, a sulfone group, a sulfoxide group and—Se(O)R³⁹, wherein N, O, S, Se and P each represents a coordinationatom;

B is selected from the group consisting of a nitrogen atom, anitrogen-containing group, a phosphor-containing group and a C₁-C₃₀hydrocarbyl;

D is selected from the group consisting of a nitrogen atom, an oxygenatom, a sulfur atom, a selenium atom, a phosphor atom, anitrogen-containing group, a phosphor-containing group, a C₁-C₃₀hydrocarbyl, a sulfone group, a sulfoxide group,

—N(O)R²⁵R²⁶,

and —P(O)R³²(OR³³), wherein N, O, S, Se and P each represents acoordination atom;

E is selected from the group consisting of a nitrogen-containing group,an oxygen-containing group, a sulfur-containing group, aselenium-containing group, a phosphor-containing group and a cyano group(—CN), wherein N, O, S, Se and P each represents a coordination atom;

F is selected from the group consisting of a nitrogen atom, anitrogen-containing group, an oxygen-containing group, asulfur-containing group, a selenium-containing group and aphosphor-containing group, wherein N, O, S, Se and P each represents acoordination atom;

G is selected from the group consisting of a C₁-C₃₀ hydrocarbyl, asubstituted C₁-C₃₀ hydrocarbyl and an inert functional group;

Y is selected from the group consisting of a nitrogen-containing group,an oxygen-containing group, a sulfur-containing group, aselenium-containing group and a phosphor-containing group, wherein N, O,S, Se and P each represents a coordination atom;

Z is selected from the group consisting of a nitrogen-containing group,an oxygen-containing group, a sulfur-containing group, aselenium-containing group, a phosphor-containing group and a cyano group(—CN), for example, —NR²³R²⁴, —N(O)R²⁵R²⁶, —PR²⁸R²⁹, —P(O)R³⁰R³¹, —OR³⁴,—SR³⁵, —S(O)R³⁶, —SeR³⁸ or —Se(O)R³⁹, wherein N, O, S, Se and P eachrepresents a coordination atom;

→ represents a single bond or a double bond;

— represents a covalent bond or an ionic bond;

R¹ to R⁴, R⁶ to R³⁶, R³⁸ and R³⁹ are each independently selected fromthe group consisting of a hydrogen atom, a C₁-C₃₀ hydrocarbyl, asubstituted C₁-C₃₀ hydrocarbyl (preferably a halogenated hydrocarbyl,for example —CH₂Cl and —CH₂CH₂Cl) and an inert functional group, whereinthese groups may be identical to or different from one another, and anyadjacent groups (for example R¹ and R², R⁶ and R⁷, R⁷ and R⁸, R⁸ and R⁹,R¹³ and R¹⁴R¹⁴, and R¹⁵, R¹⁵ and R¹⁶, R¹⁸ and R¹⁹, R¹⁹ and R²⁰, R²⁰ andR²¹, R²³ and R²⁴, or R²⁵ and R²⁶) may form a bond or a ring (preferablyan aromatic ring, for example a unsubstituted benzene ring or a benzenering substituted by one to four of a C₁-C₃₀ hydrocarbyl, a substitutedC₁-C₃₀ hydrocarbyl (preferably a halogenated hydrocarbyl, for example—CH₂Cl and —CH₂CH₂Cl) or an inert functional group) with one another;and

R⁵ is selected from the group consisting of the lone pair electron onthe nitrogen atom, a hydrogen atom, a C₁-C₃₀ hydrocarbyl, a substitutedC₁-C₃₀ hydrocarbyl, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a selenium-containing group, and aphosphor-containing group, with the proviso that when R⁵ is theoxygen-containing group, the sulfur-containing group, thenitrogen-containing group, the selenium-containing group or thephosphor-containing group, N, O, S, P and Se in the group R⁵ each canact as a coordination atom to coordinate with the central metal atom(the Group IVB metal atom).

According to this invention, in all of the aforesaid formulae, ifnecessary, any two or more adjacent groups (for example R²¹ and thegroup Z, or R¹³ and the group Y) may form a ring with one another,preferably a C₆-C₃₀ aromatic heteroatomic ring containing the heteroatom originated from the group Z or Y, for example a pyridine ring,wherein the aromatic heteroatomic ring is optionally substituted by oneor more substituent(s) selected from the group consisting of a C₁-C₃₀hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl and an inert functionalgroup.

In the context of this invention, the halogen atom is selected from thegroup consisting of F, Cl, Br and I the nitrogen-containing group isselected from the group consisting of

—NR²³R²⁴, -T-NR²³R²⁴ and —N(O)R²⁵R²⁶, the phosphor-containing group isselected from the group consisting of

—PR²⁸R²⁹, —P(O)R³⁰R³¹ and —P(O)R³²(OR³³), the oxygen-containing group isselected from the group consisting of hydroxy, —OR³⁴ and -T-OR³⁴, thesulfur-containing group is selected from the group consisting of —SR³⁵,-T-SR³⁵, —S(O)R³⁶ and -T-SO₂R³⁷, the selenium-containing group isselected from the group consisting of —SeR³⁸, -T-SeR³⁸, —Se(O)R³⁹ and-T-Se(O)R³⁹, the group T is selected from the group consisting of aC₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl and an inertfunctional group, and R³⁷ is selected from the group consisting of ahydrogen atom, a C₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyland an inert functional group.

In the context of this invention, the C₁-C₃₀ hydrocarbyl is selectedfrom the group consisting of a C₁-C₃₀ alkyl group (for example a C₁-C₆alkyl group, for example isobutyl group), a C₇-C₅₀ alkylaryl group (forexample tolyl, xylyl, diisobutyl phenyl), a C₇-C₅₀ aralkyl group (forexample benzyl), a C₃-C₃₀ cyclic alkyl group, a C₂-C₃₀ alkenyl group, aC₂-C₃₀ alkynyl group, a C₆-C₃₀ aryl group (for example phenyl, naphthyl,anthracyl), a C₈-C₃₀ fused-ring group and a C₄-C₃₀ heterocyclic group,wherein the heterocyclic group contains 1 to 3 hetero atom(s) selectedfrom the group consisting of a nitrogen atom, an oxygen atom and asulfur atom, including for example a pyridyl group, a pyrrolyl group, afuranyl group and a thienyl group.

In the context of this invention, depending on the nature of therelevant groups to which the C₁-C₃₀ hydrocarbyl bond, it is obvious to aperson skilled in the art that the C₁-C₃₀ hydrocarbyl may intend aC₁-C₃₀ hydrocarbon-diyl (a bivalent group, or referred to as a C₁-C₃₀hydrocarbylene group) or a C₁-C₃₀ hydrocarbon-triyl (a trivalent group).

In the context of this invention, the substituted C₁-C₃₀ hydrocarbylintends the aforesaid C₁-C₃₀ hydrocarbyl having one or more inertsubstituent(s). By inert, it means that these inert substituents willnot substantially interfere with the coordination process between theaforesaid coordination groups (i.e. the aforesaid groups A, D, E, F, Yand Z, or further, if applicable, the group R⁵) and the central metalatom (i.e. the aforesaid Group IVB metal atom). In other words,restricted by the specific chemical structure of the presentnonmetallocene ligand, these substituents are incapable of or have nochance (due to for example steric hindrance) to coordinate with theGroup IVB metal atom to form a coordination bond therewith. Generally,the inert substituent refers to the aforesaid halogen atom or C₁-C₃₀alkyl group (for example a C₁-C₆ alkyl group, for example isobutylgroup).

In the context of this invention, the term “inert functional group” doesnot comprise the aforesaid C₁-C₃₀ hydrocarbyl or substituted C₁-C₃₀hydrocarbyl in its concept. As the inert functional group, the halogenatom, the oxygen-containing group, the nitrogen-containing group, asilicon-containing group, a germanium-containing group, thesulfur-containing group, a tin-containing group, a C₁-C₁₀ ester group ora nitro group (—NO₂) can be exemplified.

In the context of this invention, restricted by the specific structureof the present nonmetallocene ligand, the inert functional group ischaracterized that:

(1) it will not interfere with the coordination process between theaforesaid group A, D, E, F, Y or Z and the Group IVB metal atom, and

(2) its capability to form a coordination bond with the Group IVB metalatom is inferior to the capability of the aforesaid group A, D, E, F, Yor Z to form a coordination bond with the Group IVB metal atom and willnot displace the formed coordination between the Group IVB metal atomand these groups.

In the context of this invention, the silicon-containing group isselected from the group consisting of —SiR⁴²R⁴³R⁴⁴, and -T-SiR⁴⁵, thegermanium-containing group is selected from the group consisting of—GeR⁴⁶R⁴⁷R⁴⁸, and -T-GeR⁴⁹, the tin-containing group is selected fromthe group consisting of —SnR⁵⁰R⁵¹R⁵², -T-SnR⁵³ and -T-Sn(O)R⁵⁴, R⁴² toR⁵⁴ are each independently selected from the group consisting of ahydrogen atom, the C₁-C₃₀ hydrocarbyl, the substituted C₁-C₃₀hydrocarbyl and the inert functional group, wherein these groups may beidentical to or different from one another, and any adjacent groups mayform a bond or a ring with one another, and the group T is defined asaforesaid.

As the nonmetallocene ligand, the following compounds can be furtherexemplified.

As the nonmetallocene ligand, the following compounds can be furtherexemplified.

As the nonmetallocene ligand, the following compounds can be furtherexemplified.

As the nonmetallocene ligand, the following compounds can be furtherexemplified.

The nonmetallocene ligands could be used with one kind or as a mixtureof two or more kinds at any ratio therebetween.

According to this invention, the nonmetallocene ligand does notcorrespond to the di-ether compound conventionally used in this field asan electron donor compound.

According to this invention, the nonmetallocene ligand can be producedin line with any process known in this field by a person skilled in theart. For the details of the process, one can refer to for exampleWO03/010207 or the Chinese Patent Nos. ZL01126323.7 and ZL02110844.7.All the references cited herein are incorporated by reference in theirentireties.

According to the first embodiment of this invention, by directly dryingthe magnesium compound solution, a freely flowable solid product can beobtained, which corresponds to the modified carrier of this invention.

According to the first embodiment of this invention, in order todirectly dry the magnesium compound solution, any conventional process,for example, drying under an inert gas atmosphere, vacuum drying orvacuum drying under heat, can be used, preferably vacuum drying underheat. The drying is generally conducted at a temperature 5 to 15° C.lower than the boiling point of any solvent in the magnesium compoundsolution, which would be a temperature of 30 to 160° C. or 60 to 130°C., while the duration for the drying is generally, not limiting to, 2to 24 hours.

According to the third or fourth embodiment of this invention, theporous carrier is mixed with the magnesium compound solution, wherebyobtaining the slurry.

According to this invention, mixing of the porous carrier with themagnesium compound solution could be conducted by using any conventionalprocess, without any specific limitation. For example, the mixing couldbe conducted by for example at a temperature ranging from the normaltemperature to the temperature at which the magnesium compound solutionis prepared, metering the porous carrier into the magnesium compoundsolution, or metering the magnesium compound solution into the porouscarrier, and then mixing with each other for 0.1 to 8 hours, such as 0.5to 4 hours, such as 1 to 2 hours, if necessary, under stirring.

According to this invention, as the amount of the porous carrier to beused, it is desirable that the ratio by weight of the magnesium compound(based on the magnesium compound solid contained in the magnesiumcompound solution) to the porous carrier is 1:0.1-20, preferably1:0.5-10, more preferably 1:1-5.

The resultant slurry is a slurry system. Though it is not alwaysnecessary, it is preferably for the slurry to stand in a sealed statefor a determined duration after preparation, so as to secure uniformityof the system, wherein the duration could be 2 to 48 hours, such as 4 to24 hours, such as 6 to 18 hours.

The porous carrier is further described as follows.

According to this invention, as the porous carrier, the organic orinorganic porous solid conventionally used in this field as the carrierfor producing a supported catalyst can be exemplified.

Specifically, as the organic porous solid, olefin homopolymers orcopolymers, vinyl alcohol homopolymers or copolymers, cyclodextrins,polyesters or co-polyesters, polyamides or co-polyamides, vinyl chloridehomopolymers or copolymers, acrylic ester homopolymers or copolymers,methacrylic ester homopolymers or copolymers, styrene homopolymers orcopolymers, and partly crosslinked products of these homopolymers orcopolymers can be exemplified, preferably partly crosslinked styrenepolymers (for example one having a crosslinking degree of from 2% toless than 100%).

According to a further embodiment of this invention, the organic poroussolid has one or more active functional group(s) for example selectedfrom the group consisting of a hydroxyl group, a primary amino group, asecondary amino group, a sulfonic acid group, a carboxyl group, an amidogroup, a N-mono substituted amido group, a sulfonamido group, a N-monosubstituted sulfonamido group, a mercapto group, an imido group and ahydrazide group, on its surface, wherein the carboxyl group or thehydroxyl group is preferred.

According to a further embodiment of this invention, the organic poroussolid is subjected to a thermal activation before use. The thermalactivation can be conducted in a normal way. For example, the organicporous solid is treated by heat under a reduced pressure or under aninert gas atmosphere. By an inert gas atmosphere herein, it means thatthere exists no component capable of reacting with the organic poroussolid in the gas atmosphere, or if does exist, only at a rather minoramount. As the inert gas atmosphere, a nitrogen gas or rare gasatmosphere can be exemplified, preferably a nitrogen gas atmosphere. Inview of the poor heat resistance, the thermal activation in connectionwith the organic porous solid should be conducted with the proviso thatthe inherent structure and composition of the organic porous solid willnot be destroyed. Generally, the temperature at which the thermalactivation is conducted is from 50 to 400° C., preferably 100-250° C.,while the duration for the thermal activation is from 1 to 24 hours,preferably 2 to 12 hours. After thermal activation, the organic poroussolid should be stored under a positive pressure under an inert gasatmosphere before use.

As the inorganic porous solid, a refractory oxide of a Group IIA, IIIA,IVA or IVB metal in the Periodic Table of Elements (for example silica(also known as silicon dioxide or silica gel), alumina, magnesia,titania, zirconia, or thorium oxide), or a refractory composite oxide ofany of these metals (for example, silica-alumina, magnesia-alumina,titania-silica, titania-magnesia, or titania-alumina), and clay,molecular sieve (for example ZSM-5 or MCM-41), mica, montmorillonite,bentonite or kieselguhr can be exemplified. As the inorganic poroussolid, the oxide produced by high temperature hydrolysis of a gaseousmetal halide or a gaseous silicon compound, for example silica producedby high temperature hydrolysis of silicon tetrachloride, or aluminaproduced by high temperature hydrolysis of AlCl3 can be furtherexemplified.

As the inorganic porous solid, preference is given to silica, alumina,magnesia, silica-alumina, magnesia-alumina, titania-silica, titaniumoxide, molecular sieve and montmorillonite, more preferably silica.

According to this invention, suitable silica can be produced by anyconventional process, or is any commercially available one. For example,Grace 955, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046,Davsion Syloid 245 and Aerosil 812 from the Grace company, ES70, ES70X,ES70Y, ES70W, ES757, EP10X and EP11 from the Ineos company, or CS-2133and MS-3040 from the PQ company can be exemplified.

According to a further embodiment of this invention, the inorganicporous solid has an active functional group on its surface, for examplea hydroxyl group.

According to a further embodiment of this invention, the inorganicporous solid is subjected to a thermal activation before use. Thethermal activation can be conducted in a normal way. For example, theinorganic porous solid is treated by heat under a reduced pressure orunder an inert gas atmosphere. By an inert gas atmosphere herein, itmeans that there exists no component capable of reacting with theinorganic porous solid in the gas atmosphere, or if does exist, only ata rather minor amount. As the inert gas atmosphere, a nitrogen gas orrare gas atmosphere can be exemplified, preferably a nitrogen gasatmosphere. Generally, the temperature at which the thermal activationis conducted is from 200 to 800° C., preferably 400-700° C., preferably400-650° C., while the duration for the thermal activation is from 0.5to 24 hours, preferably 2 to 12 hours, preferably 4 to 8 hours. Afterthermal activation, the inorganic porous solid should be stored under apositive pressure under an inert gas atmosphere before use.

According to this invention, the surface area (measured by the BETmethod) of the porous carrier is generally, but not limiting to, 10 to1000 m²/g, or 100 to 600 m²/g. The pore volume (measured by the nitrogenadsorption method) of the porous carrier is generally 0.1 to 4 cm³/g, or0.2 to 2 cm³/g. The average particle size (measured by a laser particlesize analyzer) of the porous carrier is generally 1 to 500 μm, or 1 to100 μm.

According to this invention, the porous carrier can present in any form,for example, fine powder, particulate, sphere, aggregate, or other form.

According to the third embodiment of this invention, by directly dryingthe slurry, or by filtering, washing and drying the slurry, preferablydirectly drying, a freely flowable solid product can be obtained, whichcorresponds to the composite carrier of this invention.

According to the third embodiment of this invention, in the case ofdirectly drying the slurry, any conventional process, for example,drying under an inert gas atmosphere, vacuum drying or vacuum dryingunder heat, can be used, preferably vacuum drying under heat. The dryingis generally conducted at a temperature 5 to 15° C. lower than theboiling point of any solvent in the slurry, which would be a temperatureof 30 to 160° C. or 60 to 130° C., while the duration for the drying isgenerally, not limiting to, 2 to 24 hours.

According to the third embodiment of this invention, in case offiltering, washing and drying of the slurry, there is no limitation tothe process for filtering, washing or drying, and any conventionalprocess conventionally used in this field can be used as needed.According to this invention, the washing can be generally conducted for1 to 6 times, preferable 2 to 3 times. Herein, the solvent for washingcan be the same as or different from that contained in the slurry. Thedrying can be conducted in a conventional way, preferably as describedin connection with the case of directly drying the slurry.

According to the second embodiment of this invention, by metering intothe magnesium compound solution a precipitating agent, solid matter(solid product) is precipitated out of the magnesium compound solution,whereby obtaining the modified carrier.

Further, according to the fourth embodiment of this invention, bymetering into the slurry a precipitating agent, solid matter (solidproduct) is precipitated out of the slurry, whereby obtaining thecomposite carrier of this invention.

The precipitating agent is further described as follows.

According to this invention, the term “precipitating agent” is explainedin a normal sense as known in this field, and refers to a chemicallyinert liquid capable of lowering the solubility of a solute (for examplethe magnesium compound) in its solution to the degree that said soluteprecipitates from the solution as solid matter.

According to this invention, as the precipitating agent, a solvent thatrepresents as a poor solvent for the magnesium compound while as a goodsolvent for the solvent for dissolving the magnesium compound can beexemplified. For example, an alkane, a cyclic alkane, a halogenatedalkane and a halogenated cyclic alkane can be further exemplified.

As the alkane, exemplified is pentane, hexane, heptane, octane, nonaneand decane, and the like, such as hexane, heptane and decane, such ashexane.

As the cyclic alkane, exemplified is cyclohexane, cyclo pentane, cycloheptane, cyclo decane, cyclo nonane, and the like, such as cyclo hexane.

As the halogenated alkane, exemplified is dichloro methane, dichlorohexane, dichloro heptane, trichloro methane, trichloro ethane, trichlorobutane, dibromo methane, dibromo ethane, dibromo heptane, tribromomethane, tribromo ethane, tribromo butane, and the like.

As the halogenated cyclic alkane, exemplified is chlorinated cyclopentane, chlorinated cyclo hexane, chlorinated cyclo heptane,chlorinated cyclo octane, chlorinated cyclo nonane, chlorinated cyclodecane, brominated cyclo pentane, brominated cyclo hexane, brominatedcyclo heptane, brominated cyclo octane, brominated cyclo nonane,brominated cyclo decane, and the like.

The precipitating agent can be used with one kind or as a mixture of twoor more kinds at any ratio therebetween.

The precipitating agent could be added all at once or dropwise, such asall at once. During the precipitation, any stirring means could be usedto facilitate uniform dispersion of the precipitating agent throughoutthe slurry or the magnesium compound solution, and eventually facilitateprecipitation of the solid product. The stirring means could be in anyform, for example, as a stirring paddle, whose rotational speed could be10 to 1000 r/min.

There is no limitation as to the amount of the precipitating agent to beused, generally, the ratio by volume of the precipitating agent to thesolvent for dissolving the magnesium compound is 1:0.2˜5, preferably1:0.5˜2, more preferably 1:0.8˜1.5.

There is no limitation as to the temperature at which the precipitatingagent is, such as the normal temperature. Further, the precipitationprocess can be generally conducted at the normal temperature as well.

After completely precipitated, the thus obtained solid product isfiltered, washed and dried. There is no limitation to the process forfiltering, washing or drying, and any conventional processconventionally used in this field can be used as needed.

If needed, the washing can be generally conducted for 1 to 6 times,preferable 2 to 3 times. Herein, the solvent for washing can be the sameas or different from the precipitating agent.

The drying can be conducted in line with a conventional process, forexample, drying under an inert gas atmosphere, vacuum drying or vacuumdrying under heat, preferably drying under an inert gas atmosphere orvacuum drying under heat, most preferably vacuum drying under heat.

The drying is generally conducted at a temperature ranging from thenormal temperature to 100° C. for a duration by which the mass in dryingwill not loss weight any further. For example, in the case whereintetrahydrofuran is used as the solvent for dissolving the magnesiumcompound, the drying is generally conducted at about 80° C. under vacuumfor a duration of 2 to 12 hours, while toluene is used as the solventfor dissolving the magnesium compound, the drying is generally conductedat about 100° C. under vacuum for a duration of 4 to 24 hours.

Then, according to the first to fourth embodiments of this invention,the composite carrier or the modified carrier is treated with a chemicaltreating agent selected from the group consisting of Group IVB metalcompounds (referred to as the chemical treating step hereinafter) so asto obtain the supported nonmetallocene catalyst of this invention.

According to this invention, by subjecting the composite carrier or themodified carrier to a chemical treatment with the chemical treatingagent, reaction occurs between the nonmetallocene ligand contained inthe composite carrier or the modified carrier with the chemical treatingagent, so as to in-situ form a nonmetallocene complex on the carrier(hereinafter referred to as the in-situ supporting reaction), wherebyobtaining the supported nonmetallocene catalyst according to thisinvention.

The chemical treating agent is further described as follows.

According to this invention, a Group IVB metal compound is used as thechemical treating agent.

As the Group IVB metal compound, exemplified is a Group IVB metalhalide, a Group IVB metal alkylate, a Group IVB metal alkoxylate, aGroup IVB metal alkyl halide, and a Group IVB metal alkoxy halide.

As the Group IVB metal halide, the Group IVB metal alkylate, the GroupIVB metal alkoxylate, the Group IVB metal alkyl halide and the Group IVBmetal alkoxy halide, exemplified is a compound having the followinggeneral formula (IV).M(OR¹)_(m)X_(n)R² _(4-m-n)  (IV)wherein,

m is 0, 1, 2, 3, or 4,

n is 0, 1, 2, 3, or 4,

M is a Group IVB metal in the Periodic Table of Elements, for example,titanium, zirconium, hafnium and the like,

X is a halogen atom, for example, F, Cl, Br, and I, and

R¹ and R² each independently is selected from the group consisting of aC₁-C₁₀ alkyl, for example, methyl, ethyl, propyl, n-butyl, isobutyl andthe like, R¹ and R² could be identical to or different from each other.

Specifically, the Group IVB metal halide could be exemplified as forexample, titanium tetrafluoride (TiF₄), titanium tetrachloride (TiCl₄),titanium tetrabromide (TiBr₄), titanium tetraiodide (TiI₄), zirconiumtetrafluoride (ZrF₄), zirconium tetrachloride (ZrCl₄), zirconiumtetrabromide (ZrBr₄), zirconium tetraiodide (ZrI₄), hafniumtetrafluoride (HfF₄), hafnium tetrachloride (HfCl₄), hafniumtetrabromide (HfBr₄), hafnium tetraiodide (HfI₄).

As the Group IVB metal alkylate, exemplified is tetramethyl titanium(Ti(CH₃)₄), tetraethyl titanium (Ti(CH₃CH₂)₄), tetraisobutyl titanium(Ti(i-C₄H₉)₄), tetran-butyl titanium (Ti(C₄H₉)₄), triethyl methyltitanium (Ti(CH₃)(CH₃CH₂)₃), diethyl dimethyl titanium(Ti(CH₃)₂(CH₃CH₂)₂), trimethyl ethyl titanium (Ti(CH₃)₃(CH₃CH₂)),triisobutyl methyl titanium (Ti(CH₃)(i-C₄H₉)₃), diisobutyl dimethyltitanium (Ti(CH₃)₂(i-C₄H₉)₂), trimethyl isobutyl titanium(Ti(CH₃)₃(i-C₄H₉)), triisobutyl ethyl titanium (Ti(CH₃CH₂)(i-C₄H₉)₃),diisobutyl diethyl titanium (Ti(CH₃CH₂)₂(i-C₄H₉)₂), triethyl isobutyltitanium (Ti(CH₃CH₂)₃(i-C₄H₉)), trin-butyl methyl titanium(Ti(CH₃)(C₄H₉)₃), din-butyl dimethyl titanium (Ti(CH₃)₂(C₄H₉)₂),trimethyl n-butyl titanium (Ti(CH₃)₃(C₄H₉)), trin-butyl methyl titanium(Ti(CH₃CH₂)(C₄H₉)₃), din-butyl diethyl titanium (Ti(CH₃CH₂)₂(C₄H₉)₂),triethyl n-butyl titanium (Ti(CH₃CH₂)₃(C₄H₉)), and so on,

tetramethyl zirconium (Zr(CH₃)₄), tetraethyl zirconium (Zr(CH₃CH₂)₄),tetraisobutyl zirconium (Zr(i-C₄H₉)₄), tetran-butyl zirconium(Zr(C₄H₉)₄), triethyl methyl zirconium (Zr(CH₃)(CH₃CH₂)₃), diethyldimethyl zirconium (Zr(CH₃)₂(CH₃CH₂)₂), trimethyl ethyl zirconium(Zr(CH₃)₃(CH₃CH₂)), triisobutyl methyl zirconium (Zr(CH₃)(i-C₄H₉)₃),diisobutyl dimethyl zirconium (Zr(CH₃)₂(i-C₄H₉)₂), trimethyl isobutylzirconium (Zr(CH₃)₃(i-C₄H₉)), triisobutyl ethyl zirconium(Zr(CH₃CH₂)(i-C₄H₉)₃), diisobutyl diethyl zirconium(Zr(CH₃CH₂)₂(i-C₄H₉)₂), triethyl isobutyl zirconium(Zr(CH₃CH₂)₃(i-C₄H₉)), trin-butyl methyl zirconium (Zr(CH₃)(C₄H₉)₃),din-butyl dimethyl zirconium (Zr(CH₃)₂(C₄H₉)₂), trimethyl n-butylzirconium (Zr(CH₃)₃(C₄H₉)), trin-butyl methyl zirconium(Zr(CH₃CH₂)(C₄H₉)₃), din-butyl diethyl zirconium (Zr(CH₃CH₂)₂(C₄H₉)₂),triethyl n-butyl zirconium (Zr(CH₃CH₂)₃(C₄H₉)), and so on,

tetramethyl hafnium (Hf(CH₃)₄), tetraethyl hafnium (Hf(CH₃CH₂)₄),tetraisobutyl hafnium (Hf(i-C₄H₉)₄), tetran-butyl hafnium (Hf(C₄H₉)₄),triethyl methyl hafnium (Hf(CH₃)(CH₃CH₂)₃), diethyl dimethyl hafnium(Hf(CH₃)₂(CH₃CH₂)₂), trimethyl ethyl hafnium (Hf(CH₃)₃(CH₃CH₂)),triisobutyl methyl hafnium (Hf(CH₃)(i-C₄H₉)₃), diisobutyl dimethylhafnium (Hf(CH₃)₂(i-C₄H₉)₂), trimethyl isobutyl hafnium(Hf(CH₃)₃(i-C₄H₉)), triisobutyl ethyl hafnium (Hf(CH₃CH₂)(i-C₄H₉)₃),diisobutyl diethyl hafnium (Hf(CH₃CH₂)₂(i-C₄H₉)₂), triethyl isobutylhafnium (Hf(CH₃CH₂)₃(i-C₄H₉)), trin-butyl methyl hafnium(Hf(CH₃)(C₄H₉)₃), din-butyl dimethyl hafnium (Hf(CH₃)₂(C₄H₉)₂),trimethyl n-butyl hafnium (Hf(CH₃)₃(C₄H₉)), trin-butyl methyl hafnium(Hf(CH₃CH₂)(C₄H₉)₃), din-butyl diethyl hafnium (Hf(CH₃CH₂)₂(C₄H₉)₂),triethyl n-butyl hafnium (Hf(CH₃CH₂)₃(C₄H₉)), and so on.

As the Group IVB metal alkoxylate, exemplified is tetramethoxy titanium(Ti(OCH₃)₄), tetraethoxy titanium (Ti(OCH₃CH₂)₄), tetraisobutoxytitanium (Ti(i-OC₄H₉)₄), tetran-butoxy titanium (Ti(OC₄H₉)₄), triethoxymethoxy titanium (Ti(OCH₃)(OCH₃CH₂)₃), diethoxy dimethoxy titanium(Ti(OCH₃)₂(OCH₃CH₂)₂), trimethoxy ethoxy titanium (Ti(OCH₃)₃(OCH₃CH₂)),triisobutoxy methoxy titanium (Ti(OCH₃)(i-OC₄H₉)₃), diisobutoxydimethoxy titanium (Ti(OCH₃)₂(i-OC₄H₉)₂), trimethoxy isobutoxy titanium(Ti(OCH₃)₃(i-OC₄H₉)), triisobutoxy ethoxy titanium(Ti(OCH₃CH₂)(i-OC₄H₉)₃), diisobutoxy diethoxy titanium(Ti(OCH₃CH₂)₂(i-OC₄H₉)₂), triethoxy isobutoxy titanium(Ti(OCH₃CH₂)₃(i-OC₄H₉)), tri-n-butoxy methoxy titanium(Ti(OCH₃)(OC₄H₉)₃), din-butoxy dimethoxy titanium (Ti(OCH₃)₂(OC₄H₉)₂),trimethoxy n-butoxy titanium (Ti(OCH₃)₃(OC₄H₉)), tri-n-butoxy methoxytitanium (Ti(OCH₃CH₂)(OC₄H₉)₃), din-butoxy diethoxy titanium(Ti(OCH₃CH₂)₂(OC₄H₉)₂), triethoxy n-butoxy titanium(Ti(OCH₃CH₂)₃(OC₄H₉)), and so on,

tetramethoxy zirconium (Zr(OCH₃)₄), tetraethoxy zirconium(Zr(OCH₃CH₂)₄), tetraisobutoxy zirconium (Zr(i-OC₄H₉)₄), tetran-butoxyzirconium (Zr(OC₄H₉)₄), triethoxy methoxy zirconium(Zr(OCH₃)(OCH₃CH₂)₃), diethoxy dimethoxy zirconium(Zr(OCH₃)₂(OCH₃CH₂)₂), trimethoxy ethoxy zirconium (Zr(OCH₃)₃(OCH₃CH₂)),triisobutoxy methoxy zirconium (Zr(OCH₃)(i-OC₄H₉)₃), diisobutoxydimethoxy zirconium (Zr(OCH₃)₂(i-OC₄H₉)₂), trimethoxy isobutoxyzirconium (Zr(OCH₃)₃(i-C₄H₉)), triisobutoxy ethoxy zirconium(Zr(OCH₃CH₂)(i-OC₄H₉)₃), diisobutoxy diethoxy zirconium(Zr(OCH₃CH₂)₂(i-OC₄H₉)₂), triethoxy isobutoxy zirconium(Zr(OCH₃CH₂)₃(i-OC₄H₉)), tri-n-butoxy methoxy zirconium(Zr(OCH₃)(OC₄H₉)₃), din-butoxy dimethoxy zirconium (Zr(OCH₃)₂(OC₄H₉)₂),trimethoxy n-butoxy zirconium (Zr(OCH₃)₃(OC₄H₉)), tri-n-butoxy methoxyzirconium (Zr(OCH₃CH₂)(OC₄H₉)₃), din-butoxy diethoxy zirconium(Zr(OCH₃CH₂)₂(OC₄H₉)₂), triethoxy n-butoxy zirconium(Zr(OCH₃CH₂)₃(OC₄H₉)), and so on,

tetramethoxy hafnium (Hf(OCH₃)₄), tetraethoxy hafnium (Hf(OCH₃CH₂)₄),tetraisobutoxy hafnium (Hf(i-OC₄H₉)₄), tetran-butoxy hafnium(Hf(OC₄H₉)₄), triethoxy methoxy hafnium (Hf(OCH₃)(OCH₃CH₂)₃), diethoxydimethoxy hafnium (Hf(OCH₃)₂(OCH₃CH₂)₂), trimethoxy ethoxy hafnium(Hf(OCH₃)₃(OCH₃CH₂)), triisobutoxy methoxy hafnium (Hf(OCH₃)(i-OC₄H₉)₃),diisobutoxy dimethoxy hafnium (Hf(OCH₃)₂(i-OC₄H₉)₂), trimethoxyisobutoxy hafnium (Hf(OCH₃)₃(i-OC₄H₉)), triisobutoxy ethoxy hafnium(Hf(OCH₃CH₂)(i-OC₄H₉)₃), diisobutoxy diethoxy hafnium(Hf(OCH₃CH₂)₂(i-OC₄H₉)₂), triethoxy isobutoxy hafnium(Hf(OCH₃CH₂)₃(i-C₄H₉)), tri-n-butoxy methoxy hafnium (Hf(OCH₃)(OC₄H₉)₃),din-butoxy dimethoxy hafnium (Hf(OCH₃)₂(OC₄H₉)₂), trimethoxy n-butoxyhafnium (Hf(OCH₃)₃(OC₄H₉)), tri-n-butoxy methoxy hafnium(Hf(OCH₃CH₂)(OC₄H₉)₃), din-butoxy diethoxy hafnium(Hf(OCH₃CH₂)₂(OC₄H₉)₂), triethoxy n-butoxy hafnium(Hf(OCH₃CH₂)₃(OC₄H₉)), and so on.

As the Group IVB metal alkyl halide, exemplified is trimethyl chlorotitanium (TiCl(CH₃)₃), triethyl chloro titanium (TiCl(CH₃CH₂)₃),triisobutyl chloro titanium (TiCl(i-C₄H₉)₃), trin-butyl chloro titanium(TiCl(C₄H₉)₃), dimethyl dichloro titanium (TiCl₂(CH₃)₂), diethyldichloro titanium (TiCl₂(CH₃CH₂)₂), diisobutyl dichloro titanium(TiCl₂(i-C₄H₉)₂), trin-butyl chloro titanium (TiCl(C₄H₉)₃), methyltrichloro titanium (Ti(CH₃)Cl₃), ethyl trichloro titanium(Ti(CH₃CH₂)Cl₃), isobutyl trichloro titanium (Ti(i-C₄H₉)Cl₃), n-butyltrichloro titanium (Ti(C₄H₉)Cl₃),

trimethyl bromo titanium (TiBr(CH₃)₃), triethyl bromo titanium(TiBr(CH₃CH₂)₃), triisobutyl bromo titanium (TiBr(i-C₄H₉)₃), trin-butylbromo titanium (TiBr(C₄H₉)₃), dimethyl dibromo titanium (TiBr₂(CH₃)₂),diethyl dibromo titanium (TiBr₂(CH₃CH₂)₂), diisobutyl dibromo titanium(TiBr₂(i-C₄H₉)₂), trin-butyl bromo titanium (TiBr(C₄H₉)₃), methyltribromo titanium (Ti(CH₃)Br₃), ethyl tribromo titanium (Ti(CH₃CH₂)Br₃),isobutyl tribromo titanium (Ti(i-C₄H₉)Br₃), n-butyl tribromo titanium(Ti(C₄H₉)Br₃),

trimethyl chloro zirconium (ZrCl(CH₃)₃), triethyl chloro zirconium(ZrCl(CH₃CH₂)₃), triisobutyl chloro zirconium (ZrCl(i-C₄H₉)₃),trin-butyl chloro zirconium (ZrCl(C₄H₉)₃), dimethyl dichloro zirconium(ZrCl₂(CH₃)₂), diethyl dichloro zirconium (ZrCl₂(CH₃CH₂)₂), diisobutyldichloro zirconium (ZrCl₂(i-C₄H₉)₂), trin-butyl chloro zirconium(ZrCl(C₄H₉)₃), methyl trichloro zirconium (Zr(CH₃)Cl₃), ethyl trichlorozirconium (Zr(CH₃CH₂)Cl₃), isobutyl trichloro zirconium (Zr(i-C₄H₉)Cl₃),n-butyl trichloro zirconium (Zr(C₄H₉)Cl₃),

trimethyl bromo zirconium (ZrBr(CH₃)₃), triethyl bromo zirconium(ZrBr(CH₃CH₂)₃), triisobutyl bromo zirconium (ZrBr(i-C₄H₉)₃), trin-butylbromo zirconium (ZrBr(C₄H₉)₃), dimethyl dibromo zirconium (ZrBr₂(CH₃)₂),diethyl dibromo zirconium (ZrBr₂(CH₃CH₂)₂), diisobutyl dibromo zirconium(ZrBr₂(i-C₄H₉)₂), trin-butyl bromo zirconium (ZrBr(C₄H₉)₃), methyltribromo zirconium (Zr(CH₃)Br₃), ethyl tribromo zirconium(Zr(CH₃CH₂)Br₃), isobutyl tribromo zirconium (Zr(i-C₄H₉)Br₃), n-butyltribromo zirconium (Zr(C₄H₉)Br₃),

trimethyl chloro hafnium (HfCl(CH₃)₃), triethyl chloro hafnium(HfCl(CH₃CH₂)₃), triisobutyl chloro hafnium (HfCl(i-C₄H₉)₃), trin-butylchloro hafnium (HfCl(C₄H₉)₃), dimethyl dichloro hafnium (HfCl₂(CH₃)₂),diethyl dichloro hafnium (HfCl₂(CH₃CH₂)₂), diisobutyl dichloro hafnium(HfCl₂(i-C₄H₉)₂), trin-butyl chloro hafnium (HfCl(C₄H₉)₃), methyltrichloro hafnium (Hf(CH₃)Cl₃), ethyl trichloro hafnium (Hf(CH₃CH₂)Cl₃),isobutyl trichloro hafnium (Hf(i-C₄H₉)Cl₃), n-butyl trichloro hafnium(Hf(C₄H₉)Cl₃),

trimethyl bromo hafnium (HfBr(CH₃)₃), triethyl bromo hafnium(HfBr(CH₃CH₂)₃), triisobutyl bromo hafnium (HfBr(i-C₄H₉)₃), trin-butylbromo hafnium (HfBr(C₄H₉)₃), dimethyl dibromo hafnium (HfBr₂(CH₃)₂),diethyl dibromo hafnium (HfBr₂(CH₃CH₂)₂), diisobutyl dibromo hafnium(HfBr₂(i-C₄H₉)₂), trin-butyl bromo hafnium (HfBr(C₄H₉)₃), methyltribromo hafnium (Hf(CH₃)Br₃), ethyl tribromo hafnium (Hf(CH₃CH₂)Br₃),isobutyl tribromo hafnium (Hf(i-C₄H₉)Br₃), n-butyl tribromo hafnium(Hf(C₄H₉)Br₃).

As the Group IVB metal alkoxy halide, exemplified is trimethoxy chlorotitanium (TiCl(OCH₃)₃), triethoxy chloro titanium (TiCl(OCH₃CH₂)₃),triisobutoxy chloro titanium (TiCl(i-OC₄H₉)₃), tri-n-butoxy chlorotitanium (TiCl(OC₄H₉)₃), dimethoxy dichloro titanium (TiCl₂(OCH₃)₂),diethoxy dichloro titanium (TiCl₂(OCH₃CH₂)₂), diisobutoxy dichlorotitanium (TiCl₂(i-OC₄H₉)₂), tri-n-butoxy chloro titanium (TiCl(OC₄H₉)₃),methoxy trichloro titanium (Ti(OCH₃)Cl₃), ethoxy trichloro titanium(Ti(OCH₃CH₂)Cl₃), isobutoxy trichloro titanium (Ti(i-C₄H₉)Cl₃), n-butoxytrichloro titanium (Ti(OC₄H₉)Cl₃),

trimethoxy bromo titanium (TiBr(OCH₃)₃), triethoxy bromo titanium(TiBr(OCH₃CH₂)₃), triisobutoxy bromo titanium (TiBr(i-OC₄H₉)₃),tri-n-butoxy bromo titanium (TiBr(OC₄H₉)₃), dimethoxy dibromo titanium(TiBr₂(OCH₃)₂), diethoxy dibromo titanium (TiBr₂(OCH₃CH₂)₂), diisobutoxydibromo titanium (TiBr₂(i-OC₄H₉)₂), tri-n-butoxy bromo titanium(TiBr(OC₄H₉)₃), methoxy tribromo titanium (Ti(OCH₃)Br₃), ethoxy tribromotitanium (Ti(OCH₃CH₂)Br₃), isobutoxy tribromo titanium (Ti(i-C₄H₉)Br₃),n-butoxy tribromo titanium (Ti(OC₄H₉)Br₃),

trimethoxy chloro zirconium (ZrCl(OCH₃)₃), triethoxy chloro zirconium(ZrCl(OCH₃CH₂)₃), triisobutoxy chloro zirconium (ZrCl(i-OC₄H₉)₃),tri-n-butoxy chloro zirconium (ZrCl(OC₄H₉)₃), dimethoxy dichlorozirconium (ZrCl₂(OCH₃)₂), diethoxy dichloro zirconium (ZrCl₂(OCH₃CH₂)₂),diisobutoxy dichloro zirconium (ZrCl₂(i-OC₄H₉)₂), tri-n-butoxy chlorozirconium (ZrCl(OC₄H₉)₃), methoxy trichloro zirconium (Zr(OCH₃)Cl₃),ethoxy trichloro zirconium (Zr(OCH₃CH₂)Cl₃), isobutoxy trichlorozirconium (Zr(i-C₄H₉)Cl₃), n-butoxy trichloro zirconium (Zr(OC₄H₉)Cl₃),

trimethoxy bromo zirconium (ZrBr(OCH₃)₃), triethoxy bromo zirconium(ZrBr(OCH₃CH₂)₃), triisobutoxy bromo zirconium (ZrBr(i-OC₄H₉)₃),tri-n-butoxy bromo zirconium (ZrBr(OC₄H₉)₃), dimethoxy dibromo zirconium(ZrBr₂(OCH₃)₂), diethoxy dibromo zirconium (ZrBr₂(OCH₃CH₂)₂),diisobutoxy dibromo zirconium (ZrBr₂(i-OC₄H₉)₂), tri-n-butoxy bromozirconium (ZrBr(OC₄H₉)₃), methoxy tribromo zirconium (Zr(OCH₃)Br₃),ethoxy tribromo zirconium (Zr(OCH₃CH₂)Br₃), isobutoxy tribromo zirconium(Zr(i-C₄H₉)Br₃), n-butoxy tribromo zirconium (Zr(OC₄H₉)Br₃),

trimethoxy chloro hafnium (HfCl(OCH₃)₃), triethoxy chloro hafnium(HfCl(OCH₃CH₂)₃), triisobutoxy chloro hafnium (HfCl(i-OC₄H₉)₃),tri-n-butoxy chloro hafnium (HfCl(OC₄H₉)₃), dimethoxy dichloro hafnium(HfCl₂(OCH₃)₂), diethoxy dichloro hafnium (HfCl₂(OCH₃CH₂)₂), diisobutoxydichloro hafnium (HfCl₂(i-OC₄H₉)₂), tri-n-butoxy chloro hafnium(HfCl(OC₄H₉)₃), methoxy trichloro hafnium (Hf(OCH₃)Cl₃), ethoxytrichloro hafnium (Hf(OCH₃CH₂)Cl₃), isobutoxy trichloro hafnium(Hf(i-C₄H₉)Cl₃), n-butoxy trichloro hafnium (Hf(OC₄H₉)Cl₃),

trimethoxy bromo hafnium (HfBr(OCH₃)₃), triethoxy bromo hafnium(HfBr(OCH₃CH₂)₃), triisobutoxy bromo hafnium (HfBr(i-OC₄H₉)₃),tri-n-butoxy bromo hafnium (HfBr(OC₄H₉)₃), dimethoxy dibromo hafnium(HfBr₂(OCH₃)₂), diethoxy dibromo hafnium (HfBr₂(OCH₃CH₂)₂), diisobutoxydibromo hafnium (HfBr₂(i-OC₄H₉)₂), tri-n-butoxy bromo hafnium(HfBr(OC₄H₉)₃), methoxy tribromo hafnium (Hf(OCH₃)Br₃), ethoxy tribromohafnium (Hf(OCH₃CH₂)Br₃), isobutoxy tribromo hafnium (Hf(i-C₄H₉)Br₃),n-butoxy tribromo hafnium (Hf(OC₄H₉)Br₃).

As the Group IVB metal compound, preference is given to the Group IVBmetal halide, such as TiCl₄, TiBr₄, ZrCl₄, ZrBr₄, HfCl₄ and HfBr₄, suchas TiCl₄ and ZrCl₄.

The Group IVB metal compound could be used with one kind or as a mixtureof two or more kinds at any ratio therebetween.

When the chemical treating agent presents as a liquid at the normaltemperature, the chemical treating agent can be used by directlydropwise adding a predetermined amount of the chemical treating agent toa reaction subject to be treated with said chemical treating agent (i.e.the aforesaid composite carrier or modified carrier).

When the chemical treating agent presents a solid at the normaltemperature, for ease of metering and handling, it is preferably to usesaid chemical treating agent in the form of a solution. Of course, whenthe chemical treating agent presents a liquid at the normal temperature,said chemical treating agent can be also used in the form of a solutionif needed, without any specific limitation.

In preparation of the solution of the chemical treating agent, there isno limitation as to the solvent to be used herein, as long as thesolvent is capable of dissolving the chemical treating agent.

Specifically, as the solvent, exemplified is a C₅₋₁₂ alkane or ahalogenated C₅₋₁₂ alkane, for example pentane, hexane, heptane, octane,nonane, decane, undecane, dodecane, cyclohexane, chloro pentane, chlorohexane, chloro heptane, chloro octane, chloro nonane, chloro decane,chloro undecane, chloro dodecane, chloro cyclohexane and so on,preferably pentane, hexane, decane and cyclohexane, most preferablyhexane.

The solvent could be used with one kind or as a mixture of two or morekinds at any ratio therebetween.

It is obvious that a solvent capable of extracting the magnesiumcompound is not used herein to dissolve the chemical treating agent, forexample an ether based solvent, for example tetrahydrofuran.

Further, there is no limitation as to the concentration of the chemicaltreating agent in the solution, which could be determined as needed, aslong as it is sufficient for the solution to deliver the predeterminedamount of the chemical treating agent for the chemical treatment. Asaforesaid, if the chemical treating agent presents as a liquid, it isconvenient to use said chemical treating agent as such for thetreatment, while it is also acceptable to convert it into a solutionbefore use. Generally, the molar concentration of the chemical treatingagent in its solution is, but not limiting to, 0.01 to 1.0 mol/L.

As a process for conducing the chemical treatment, exemplified is aprocess wherein, when a solid chemical treating agent (for exampleZrCl₄) is used, first of all, a solution of the chemical treating agentis prepared, then the chemical treating agent is added (preferablydropwise) at a predetermined amount to the composite carrier or modifiedcarrier to be treated, or when a liquid chemical treating agent (forexample TiCl₄) is used, it is acceptable to add (preferably dropwise) apredetermined amount of the chemical treating agent as such (or afterprepared into a solution) to the composite carrier or modified carrierto be treated. Then, the chemical treating reaction continues(facilitated by any stirring means, if necessary) at a reactiontemperature ranging from −30° C. to 60° C. (preferably −20° C. to 30°C.) for 0.5 to 24 hours, preferably 1 to 8 hours, more preferably 2 to 6hours. Then, the resultant is filtrated, washed and dried.

According to this invention, the filtrating, washing (generally for 1 to8 times, preferably 2 to 6 times, most preferably 2 to 4 times) anddrying can be conducted in a conventional manner, wherein the solventfor washing could be the same as that used for dissolving the chemicaltreating agent.

According to this invention, as the amount of the chemical treatingagent to be used, it is preferably that the ratio by molar of themagnesium compound (based on Mg and on a solid basis) to the chemicaltreating agent (based on the Group IVB metal, for example Ti) is1:0.01-1, preferably 1:0.01-0.50, more preferably 1:0.10-0.30.

According to a further embodiment of this invention, the present processfor producing a supported nonmetallocene catalyst further comprises astep of pre-treating the composite carrier or modified carrier with anassistant chemical treating agent selected from the group consisting ofan aluminoxane, an alkylaluminum and any combination thereof beforetreating the composite carrier or modified carrier with the chemicaltreating agent, referred to as the pre-treating step hereinafter. Then,the chemical treating step is conducted by using the chemical treatingagent in the same way as aforesaid, with the only difference ofreplacing the composite carrier (or the modified carrier) with the thuspre-treated composite carrier (or the thus pre-treated modifiedcarrier).

The assistant chemical treating agent is further described as follows.

According to this invention, as the assistant chemical treating agent,exemplified is aluminoxane and alkylaluminum.

As the aluminoxane, exemplified is a linear aluminoxane((R)(R)Al—(Al(R)—O)_(n)—O—Al(R)(R)) having the following formula (I),and a cyclic aluminoxane (—(Al(R)—O—)_(n+2)—) having the followingformula (II).

wherein the Rs are identical to or different from one another,preferably identical to one another, and each independently is selectedfrom the group consisting of a C₁-C₈ alkyl, preferably methyl, ethyl,and iso-butyl, most preferably methyl, n is an integer of 1 to 50,preferably of 10 to 30.

Specifically, the aluminoxane could be preferably selected from thegroup consisting of methyl aluminoxane, ethyl aluminoxane, isobutylaluminoxane and n-butyl aluminoxane, preferably methyl aluminoxane (MAO)and isobutyl aluminoxane (IBAO).

The aluminoxane could be used with one kind or as a mixture of two ormore kinds at any ratio therebetween.

As the alkylaluminum, exemplified is a compound having a general formula(III) as follows:Al(R)₃  (III)wherein the Rs are identical to or different from one another,preferably identical to one another, and is each independently selectedfrom the group consisting of a C₁-C₈ alkyl, preferably methyl, ethyl andiso-butyl, most preferably methyl.

Specifically, the alkylaluminum could be selected from the groupconsisting of trimethyl aluminum (Al(CH₃)₃), triethyl aluminum(Al(CH₃CH₂)₃), tripropyl aluminum (Al(C₃H₇)₃), triisobutyl aluminum(Al(i-C₄H₉)₃), tri-n-butyl aluminum (Al(C₄H₉)₃), triisoamyl aluminum(Al(i-C₅H₁₁)₃), tri-n-amyl aluminum (Al(C₅H₁₁)₃), trihexyl aluminum(Al(C₆H₁₃)₃), tri-iso-hexyl aluminum (Al(i-C₆H₁₃)₃), diethyl methylaluminum (Al(CH₃)(CH₃CH₂)₂) and ethyl dimethyl aluminum(Al(CH₃CH₂)(CH₃)₂), and the like, wherein preference is given totrimethyl aluminum, triethyl aluminum, triisobutyl aluminum andtripropyl aluminum, most preferably triethyl aluminum and triisobutylaluminum.

The alkylaluminum could be used with one kind or as a mixture of two ormore kinds at any ratio therebetween.

According to this invention, as the assistant chemical treating agent,used could be only the alkylaluminum or only the aluminoxane, or anymixture of the alkylaluminum and the aluminoxane. There is no limitationas to the ratio between any two or more components in the mixture, whichcould be determined as needed.

According to this invention, the assistant chemical treating agent isgenerally used in the form of a solution. In preparation of the solutionof the assistant chemical treating agent, there is no limitation as tothe solvent to be used herein, as long as the solvent can dissolve theassistant chemical treating agent.

Specifically, as the solvent, exemplified is a C₅₋₁₂ alkane or ahalogenated C₅₋₁₂ alkane, for example pentane, hexane, heptane, octane,nonane, decane, undecane, dodecane, cyclohexane, chloro pentane, chlorohexane, chloro heptane, chloro octane, chloro nonane, chloro decane,chloro undecane, chloro dodecane, chloro cyclohexane and so on,preferably pentane, hexane, decane and cyclohexane, most preferablyhexane.

It is obvious that a solvent capable of extracting the magnesiumcompound is not used herein to dissolve the assistant chemical treatingagent, for example an ether based solvent, for example tetrahydrofuran.

The solvent could be used with one kind or as a mixture of two or morekinds at any ratio therebetween.

Further, there is no limitation as to the concentration of the assistantchemical treating agent in the solution, which could be determined asneeded, as long as it is sufficient for the solution to deliver apredetermined amount of the assistant chemical treating agent for thepre-treatment.

As a process for conducing the pre-treatment, exemplified is a processwherein, first of all, a solution of the assistant chemical treatingagent is prepared, then at a temperature ranging from −30° C. to 60° C.(preferably −20° C. to 30° C.), the assistant chemical treating agentsolution (containing a predetermined amount of the assistant chemicaltreating agent) is metering (preferably dropwise) into the compositecarrier or modified carrier to be pre-treated with said assistantchemical treating agent, or the composite carrier or modified carrier ismetering into the assistant chemical treating agent solution, so as toform a reaction mixture. Then, the reaction continues (facilitated byany stirring means, if necessary) for 1 to 8 hours, preferably 2 to 6hours, more preferably 3 to 4 hours. Then, the thus obtained product isseparated from the reaction mixture by filtrating, washing (for 1 to 6times, preferably 1 to 3 times) and optional drying. Or alternatively,the thus obtained product is directly used in the next step (i.e. theaforesaid chemical treating step) in the form of the reaction mixturewithout being subject to the separation beforehand. In this case, thereaction mixture contains a certain amount of solvent, and for thisreason, the amount of the solvent involved in said next step could bereduced accordingly.

According to this invention, as the amount of the assistant chemicaltreating agent to be used, it is preferably that the ratio by molar ofthe magnesium compound (based on Mg, on a solid basis) to the assistantchemical treating agent (based on Al) is 1:0-1.0, preferably 1:0-0.5,more preferably 1:0.1-0.5.

It is known that any of the aforementioned processes and steps ispreferably carried out under a substantial water-free and oxygen-freecondition. By substantial water-free and oxygen-free condition, it meansthat water and oxygen in the system concerned is continuously controlledto be less than 10 ppm. Further, the support nonmetallocene catalystaccording to this invention, after prepared, is usually stored under asealed condition under a slightly positive pressure before use.

According to this invention, as the amount of the nonmetallocene ligandto be used, it is preferably that the ratio by molar of the magnesiumcompound (based on Mg, on a solid basis) to the nonmetallocene ligand is1:0.0001-1, preferably 1:0.0002-0.4, more preferably 1:0.0008-0.2, morepreferably 1:0.001-0.1.

According to this invention, as the amount of the solvent for dissolvingthe magnesium compound to be used, it is preferably that the ratio ofthe magnesium compound (on a solid basis) to the solvent is 1 mol:75˜400ml, preferably 1 mol:150˜300 ml, more preferably 1 mol:200˜250 ml.

According to this invention, as the amount of the chemical treatingagent to be used, it is preferably that the ratio by molar of themagnesium compound (based on Mg, on a solid basis) to the chemicaltreating agent (based on the Group IVB metal, for example Ti) is1:0.01-1, preferably 1:0.01-0.50, more preferably 1:0.10-0.30.

According to this invention, as the amount of the assistant chemicaltreating agent to be used, it is preferably that the ratio by molar ofthe magnesium compound (based on Mg, on a solid basis) to the assistantchemical treating agent (based on Al) is 1:0-1.0, preferably 1:0-0.5,more preferably 1:0.1-0.5.

According to this invention, as the amount of the alcohol to be used incombination with the solvent for dissolving the magnesium compound, itis preferably that the ratio by molar of the magnesium compound (basedon Mg and on a solid basis) to the alcohol is 1:0.02˜4.00, preferably1:0.05˜3.00, more preferably 1:0.10˜2.50.

According to this invention, as the amount of the precipitating agent tobe used, it is preferably that the ratio by volume of the precipitatingagent to the solvent for dissolving the magnesium compound is 1:0.2˜5,preferably 1:0.5˜2, more preferably 1:0.8˜1.5.

According to this invention, as the amount of the porous carrier to beused, it is preferably that the ratio by weight of the magnesiumcompound (on a solid basis) to the porous carrier is 1:0.1-20,preferably 1:0.5-10, more preferably 1:1-5.

In one embodiment, this invention relates to a supported nonmetallocenecatalyst produced in line with the process according to any of the firstto fourth embodiments of this invention, also referred to as a supportednonmetallocene catalyst for olefin polymerization.

In a further embodiment according to this invention, this inventionrelates to an olefin homopolymerization/copolymerization process,wherein the supported nonmetallocene catalyst of this invention is usedas the catalyst for olefin polymerization, to homopolymerize orcopolymerize olefin(s).

In the context of the olefin homopolymerization/copolymerization processof this invention, one can directly refer to the prior art for anycontent or information that has not been expressively and specificallydescribed hereinafter, for example, the reactor for polymerization, theamount of olefin(s), the way by which the catalyst or olefin isintroduced, unnecessiating the need of detailing same further herein.

According to the present olefin homopolymerization/copolymerizationprocess, the supported nonmetallocene catalyst of this invention is usedas the main catalyst, one or more selected from the group consisting ofan aluminoxane, an alkylaluminum, a halogenated alkyl aluminum, afluoroborane, an alkylboron and an alkylboron ammonium salt is used asthe co-catalyst, to homopolymerize or copolymerize olefin.

As the way of adding the main catalyst and the co-catalyst to thepolymerization system, exemplified is a way wherein the main catalyst isadded prior to the co-catalyst, or vise versa, or the main catalyst andthe co-catalyst contact with each other by mixing and then addedaltogether, or separately but simultaneously added. As the way of addingthe main catalyst and the co-catalyst separately, exemplified is thecase wherein the main catalyst and the co-catalyst are successivelyadded to one feed line or multiple feed lines. When the main catalystand the co-catalyst are to be added separately but simultaneously,multiple feed lines are required. For a continuous polymerization, theway of simultaneously and continuously adding to multiple feed lines ispreferred, while for a batch polymerization, the way of mixing the maincatalyst and the co-catalyst with each other and then adding to one feedline altogether, or adding to a feed line the co-catalyst and thenadding the main catalyst to the same feed line, is preferred.

There is no limitation as to how to conduct the olefinhomopolymerization/copolymerization, any conventional process known to aperson skilled in the art can be used, for example, a slurry process, anemulsion process, a solution process, a bulk process or a gas phaseprocess, preferably the slurry process or the gas phase process.

According to this invention, as the olefin to be used, exemplified is aC₂ to C₁₀ mono-olefin, a diolefin, a cyclic olefin and other ethylenicunsaturated compounds.

Specifically, as the C₂ to C₁₀ mono-olefin, exemplified is ethylene,propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene,1-decene, 1-undecene, 1-dodecene and styrene. As the cyclic olefin,exemplified is 1-cyclopentene and norbornene. As the diolefin,exemplified is 1,4-butadiene, 2,5-pentadiene, 1,6-hexadiene,norbornadiene and 1,7-octadiene. As the other ethylenic unsaturatedcompound, exemplified is vinyl acetate, and (meth)acrylate. Thisinvention prefers the homopolymerization of ethylene, or thecopolymerization of ethylene with propylene, 1-butene or 1-hexene.

According to this invention, by homopolymerization, it refers to thepolymerization of a single kind of olefin, by copolymerization, itrefers to the polymerization between two or more of the aforesaidolefins.

According to this invention, the co-catalyst is selected from the groupconsisting of an aluminoxane, an alkylaluminum, a halogenated alkylaluminum, a fluoroborane, an alkylboron and an alkylboron ammonium salt,such as the aluminoxane and the alkylaluminum.

As the aluminoxane, exemplified is a linear aluminoxane((R)(R)Al—(Al(R)—O)_(n)—O—Al(R)(R)) having the following formula (I-1),and a cyclic aluminoxane (—(Al(R)—O—)_(n+2)—) having the followingformula (II-1).

wherein the Rs are identical to or different from one another,preferably identical to one another, and each independently is selectedfrom the group consisting of a C₁-C₈ alkyl, preferably methyl, ethyl,and iso-butyl, most preferably methyl, n is an integer of 1 to 50,preferably of 10 to 30.

Specifically, the aluminoxane could be preferably selected from thegroup consisting of methyl aluminoxane, ethyl aluminoxane, isobutylaluminoxane and n-butyl aluminoxane, preferably methyl aluminoxane (MAO)and isobutyl aluminoxane (IBAO), most preferably methyl aluminoxane(MAO).

The aluminoxane could be used with one kind or as a mixture of two ormore kinds at any ratio therebetween.

As the alkylaluminum, exemplified is a compound having a general formula(III-1) as follows:Al(R)₃  (III-1)wherein the Rs are identical to or different from one another,preferably identical to one another, and is each independently selectedfrom the group consisting of a C₁-C₈ alkyl, preferably methyl, ethyl andiso-butyl, most preferably methyl.

Specifically, the alkylaluminum could be selected from the groupconsisting of trimethyl aluminum (Al(CH₃)₃), triethyl aluminum(Al(CH₃CH₂)₃), tripropyl aluminum (Al(C₃H₇)₃), triisobutyl aluminum(Al(i-C₄H₉)₃), tri-n-butyl aluminum (Al(C₄H₉)₃), triisoamyl aluminum(Al(i-C₅H₁₁)₃), tri-n-amyl aluminum (Al(C₈H₁₁)₃), tri-hexyl aluminum(Al(C₈H₁₃)₃), tri-iso-hexyl aluminum (Al(i-C₈H₁₃)₃), diethyl methylaluminum (Al(CH₃)(CH₃CH₂)₂) and ethyl dimethyl aluminum(Al(CH₃CH₂)(CH₃)₂), and the like, wherein preference is given totrimethyl aluminum, triethyl aluminum, triisobutyl aluminum andtripropyl aluminum, more preferably triethyl aluminum and triisobutylaluminum, most preferably triethyl aluminum.

The alkylaluminum could be used with one kind or as a mixture of two ormore kinds at any ratio therebetween.

As the halogenated alkyl aluminum, the fluoroborane, the alkylboron andthe alkylboron ammonium salt, exemplified is one conventionally used inthis field, but without any limitation thereto.

Further, according to this invention, the co-catalyst could be used withone kind or as a mixture of two or more kinds of the aforesaidco-catalysts at any ratio therebetween as needed, but without anylimitation thereto.

According to this invention, depending on how the olefinhomopolymerization/copolymerization is conducted, a solvent forpolymerization may be involved.

As the solvent for polymerization, one conventionally used in this fieldfor olefin homopolymerization/copolymerization can be used, but withoutany limitation thereto.

As the solvent for polymerization, exemplified is a C₄₋₁₀ alkane (forexample, butane, pentane, hexane, heptane, octane, nonane, or decane), ahalogenated C₁₋₁₀ alkane (for example, dichloro methane), an aromatichydrocarbon based solvent (for example toluene or xylene), and so on.Hexane is preferred for this purpose.

The solvent for polymerization could be used with one kind or as amixture of two or more kinds at any ratio therebetween.

According to this invention, the polymerization pressure under which theolefin homopolymerization/copolymerization is conducted is generallybetween 0.1 to 10 MPa, preferably 0.1 to 4 MPa, most preferably 1 to 3MPa, but without any limitation thereto. According to this invention,the polymerization temperature at which the olefinhomopolymerization/copolymerization is conducted is generally from −40°C. to 200° C., preferably 10° C. to 100° C., more preferably 40° C. to90° C., but without any limitation thereto.

Further, according to this invention, the olefinhomopolymerization/copolymerization can be conduct in the presence of orin the absence of hydrogen gas. If presents, the partial pressure ofhydrogen gas may generally account for 0.01 to 99% (preferably 0.01 to50%) of the polymerization pressure, but without any limitation thereto.

According to the olefin homopolymerization/copolymerization process ofthis invention, the ratio by molar of the co-catalyst (based on Al or B)to the supported nonmetallocene catalyst (based on the central metalatom M) is generally 1 to 1000:1, preferably 10 to 500:1, morepreferably 15 to 300:1, but without any limitation thereto.

Example

The present invention is further illustrated by using the followingexamples, not limiting to same.

The bulk density of the polymer was measured according to the ChineseStandard GB 1636-79 (unit: g/cm³).

The content of the Group IVB metal (for example Ti) and the content ofthe Mg element in the supported nonmetallocene catalyst were determinedby the ICP-AES method, while the content of the nonmetallocene ligandwas determined by the element analysis method.

The polymerization activity of the catalyst was calculated as follows.

Upon completion of the polymerization, the polymer product in thereactor was filtered and dried, and then weighed for its weight (bymass). Then, the polymerization activity of the catalyst was expressedby a value obtained by dividing the weight of the polymer product by theweight (by mass) of the supported nonmetallocene catalyst used (unit: kgpolymer per 1 g Cat).

The molecular weights Mw, Mn and the molecular weight distribution(Mw/Mn) of the polymer were determined at a temperature of 150° C. byusing the GPC V2000 type gel permeation chromatographer (from WATERSCo., USA), with o-trichlorobenzene as the solvent.

The viscosity averaged molecular weight of the polymer was calculated asfollows.

The intrinsic viscosity of the polymer was determined according to thestandard ASTM D4020-00 by using a high temperature dilution typeUbbelohde viscometer (with a capillary inner diameter of 0.44 mm, athermostatic bath media of 300# silicon oil, the solvent for dilution ofdecalin and a temperature of 135° C.), and then the viscosity averagedmolecular weight Mv of the polymer was calculated in line with thefollowing formula.Mv=5.37×10⁴×[η]^(1.37)

wherein, η is the intrinsic viscosity.

Example I Corresponding to the First Embodiment Example I-1

2.5 g of anhydrous magnesium chloride as the magnesium compound wasweighted, a predetermined amount of butanol and hexane were addedthereto, after heated to 60° C. to dissolve same, a predetermined amountof the nonmetallocene ligand was added thereto and then stirred at 60°C. to completely dissolve same. Then, the resultant was directly vacuumdried at 60° C., to obtain the modified carrier.

Then, to the modified carrier, 25 ml hexane as the solvent was added,and then titanium tetrachloride as the chemical treating agent wasdropwise added thereto under stirring over a period of 15 minutes. Thereaction continued at 30° C. for 4 hours, then filtered, washed withhexane for 3 times (25 ml each time), and finally vacuum dried to obtainthe supported nonmetallocene catalyst.

A compound represented by

was used as the nonmetallocene ligand.

In this example, the ratio by molar of the magnesium compound to butanolwas 1:0.5, the ratio of the magnesium compound to hexane as the solventfor dissolving the magnesium compound was 1 mol:200 ml, the ratio bymolar of the magnesium compound to the nonmetallocene ligand was1:0.004, and the ratio by molar of the magnesium compound to titaniumtetrachloride was 1:0.2.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-1.

Example I-1-1

Substantially the same as the Example I-1, except for the followingchanges:

The solvent for dissolving the magnesium compound was changed totetrahydrofuran.

In this example, the ratio by molar of the magnesium compound to butanolwas 1:0.5, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:240 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.006, andthe ratio by molar of the magnesium compound to the chemical treatingagent was 1:0.25.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-1-1.

Example I-1-2

Substantially the same as the Example I-1, except for the followingchanges:

The alcohol was changed to ethanol, the solvent for dissolving themagnesium compound was changed to ethyl benzene.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:1.64, the ratio of the magnesium compound to the solventfor dissolving the magnesium compound was 1 mol:160 ml, the ratio bymolar of the magnesium compound to the nonmetallocene ligand was1:0.004, and the ratio by molar of the magnesium compound to thechemical treating agent was 1:0.4.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-1-2.

Example I-1-3

Substantially the same as the Example I-1, except for the followingchanges:

The alcohol was changed to propanol, the magnesium compound was changedto magnesium bromide (MgBr₂), the nonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed totoluene, and the chemical treating agent was changed to zirconiumtetrachloride (ZrCl₄).

The modified carrier was obtained by directly drying under a N₂atmosphere at 120° C.

The chemical treating agent was dissolved in 25 ml toluene, and then theresultant solution was dropwise added to the modified carrier over aperiod of 15 minutes. Washing was conducted with toluene for 3 times (25ml each time), and then heated to 120° C. and vacuum dried

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:1, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:100 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.003, andthe ratio by molar of the magnesium compound to the chemical treatingagent was 1:0.5.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-1-3.

Example I-1-4

Substantially the same as the Example I-1, except for the followingchanges:

The alcohol was changed to iso-octanol, the magnesium compound waschanged to ethoxy magnesium chloride (MgCl(OC₂H₅)), the nonmetalloceneligand was changed to

the solvent for dissolving the magnesium compound was changed to chlorocyclohexane, and the chemical treating agent was changed to tetraethyltitanium (Ti(CH₃CH₂)₄).

The modified carrier was obtained by directly drying under a N₂atmosphere at 80° C.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:0.1, the ratio of the magnesium compound to the solventfor dissolving the magnesium compound was 1 mol:300 ml, the ratio bymolar of the magnesium compound to the nonmetallocene ligand was1:0.010, and the ratio by molar of the magnesium compound to thechemical treating agent was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-1-4.

Example I-1-5

Substantially the same as the Example I-1, except for the followingchanges:

The magnesium compound was changed to ethyl magnesium (Mg(C₂H₅)₂), thenonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed to xylene,and the chemical treating agent was changed to triisobutyl chlorotitanium (TiCl(i-C₄H₉)₃).

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:2.5, the ratio by molar of the magnesium compound to thenonmetallocene ligand was 1:0.16.

Example I-1-6

Substantially the same as the Example I-1, except for the followingchanges:

The magnesium compound was changed to ethoxy magnesium (Mg(OC₂H₅)₂), thenonmetallocene ligand was changed to

Example I-1-7

Substantially the same as the Example I-1, except for the followingchanges:

The magnesium compound was changed to isobutyl magnesium (Mg(i-C₄H₉)₂),the nonmetallocene ligand was changed to

Example I-1-8

Substantially the same as the Example I-1, except for the followingchanges:

The nonmetallocene ligand was changed to

Example I-2

2.5 g of anhydrous magnesium chloride as the magnesium compound wasweighted, a predetermined amount of butanol and hexane were addedthereto, after heated to 60° C. to dissolve same, a predetermined amountof the nonmetallocene ligand was added thereto and then stirred at 60°C. to completely dissolve same. Then, the resultant was directly vacuumdried at 60° C., to obtain the modified carrier.

Then, to the modified carrier, 25 ml hexane was added, and then triethylaluminum as the assistant chemical treating agent was dropwise addedthereto under stirring over a period of 15 minutes. The reactioncontinued under stirring for 1 hour, then filtered, washed with hexanefor 2 times (25 ml each time). Then, 25 ml hexane was added thereto, andthen titanium tetrachloride as the chemical treating agent was dropwiseadded thereto over a period of 15 minutes. The reaction continued at 60°C. for 4 hours, then filtered, washed with hexane for 3 times (25 mleach time), and finally vacuum dried to obtain the supportednonmetallocene catalyst.

A compound represented by

was used as the nonmetallocene ligand.

In this example, the ratio by molar of the magnesium compound to butanolwas 1:0.5, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:200 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.004, theratio by molar of the magnesium compound to titanium tetrachloride was1:0.2, and the ratio by molar of the magnesium compound to the assistantchemical treating agent was 1:0.35.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-2.

Example I-2-1

Substantially the same as the Example I-2, except for the followingchanges:

The solvent for dissolving the magnesium compound was changed totetrahydrofuran.

In this example, the ratio by molar of the magnesium compound to butanolwas 1:0.5, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:240 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.006, andthe ratio by molar of the magnesium compound to the chemical treatingagent was 1:0.25, and the ratio by molar of the magnesium compound tothe assistant chemical treating agent was 1:0.25.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-2-1.

Example I-2-2

Substantially the same as the Example I-2, except for the followingchanges:

The alcohol was changed to ethanol, the solvent for dissolving themagnesium compound was changed to ethyl benzene, the assistant chemicaltreating agent was changed to methyl aluminoxane (MAO).

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:1.64, the ratio of the magnesium compound to the solventfor dissolving the magnesium compound was 1 mol:160 ml, the ratio bymolar of the magnesium compound to the nonmetallocene ligand was1:0.004, and the ratio by molar of the magnesium compound to thechemical treating agent was 1:0.4, and the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.5.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-2-2.

Example I-2-3

Substantially the same as the Example I-2, except for the followingchanges:

The alcohol was changed to propanol, the magnesium compound was changedto magnesium bromide (MgBr₂), the nonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed totoluene, the chemical treating agent was changed to zirconiumtetrachloride (ZrCl₄), the assistant chemical treating agent was changedto triisobutyl aluminum.

The modified carrier was obtained by directly drying under a N₂atmosphere at 120° C.

The chemical treating agent was dissolved in 25 ml toluene, and then theresultant solution was dropwise added to the modified carrier over aperiod of 15 minutes. Washing was conducted with toluene for 3 times (25ml each time), and then heated to 120° C. and vacuum dried

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:1, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:100 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.003, andthe ratio by molar of the magnesium compound to the chemical treatingagent was 1:0.5, and the ratio by molar of the magnesium compound to theassistant chemical treating agent was 1:0.75.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-2-3.

Example I-2-4

Substantially the same as the Example I-2, except for the followingchanges:

The alcohol was changed to iso-octanol, the magnesium compound waschanged to ethoxy magnesium chloride (MgCl(OC₂H₅)), the nonmetalloceneligand was changed to

the solvent for dissolving the magnesium compound was changed to chlorocyclohexane, the chemical treating agent was changed to tetraethyltitanium (Ti(CH₃CH₂)₄), the assistant chemical treating agent waschanged to isobutyl aluminoxane.

The modified carrier was obtained by directly drying under a N₂atmosphere at 80° C.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:0.1, the ratio of the magnesium compound to the solventfor dissolving the magnesium compound was 1 mol:300 ml, the ratio bymolar of the magnesium compound to the nonmetallocene ligand was1:0.010, the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.15, and the ratio by molar of the magnesiumcompound to the assistant chemical treating agent was 1:1.0.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-2-4.

Example I-2-5

Substantially the same as the Example I-2, except for the followingchanges:

The magnesium compound was changed to ethyl magnesium (Mg(C₂H₅)₂), thenonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed to xylene,the chemical treating agent was changed to triisobutyl chloro titanium(TiCl(i-C₄H₉)₃), the assistant chemical treating agent was changed toethyl aluminoxane.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:2.5, the ratio by molar of the magnesium compound to thenonmetallocene ligand was 1:0.16.

Example I-2-6

Substantially the same as the Example I-2, except for the followingchanges:

The magnesium compound was changed to ethoxy magnesium (Mg(OC₂H₅)₂), thenonmetallocene ligand was changed to

the assistant chemical treating agent was changed to trimethyl aluminum.

Example I-2-7

Substantially the same as the Example I-2, except for the followingchanges:

The magnesium compound was changed to isobutyl magnesium (Mg(i-C₄H₉)₂),the nonmetallocene ligand was changed to

Example I-2-8

Substantially the same as the Example I-2, except for the followingchanges:

The nonmetallocene ligand was changed to

Example I-3 Application Example I

10 mg of the catalysts CAT-I-1, CAT-I-2, CAT-I-1-1 to CAT-I-1-4,CAT-I-2-1 to CAT-I-2-4 were respectively weighted, and added to anautoclave (5 L) together with a co-catalyst (methyl aluminoxane ortriethyl aluminum), then 2.5 L hexane was added thereto, and thestirring means (at 300 rpm) was started. After heated to 85° C.,hydrogen gas was supplied thereto all at once till 0.2 MPa, and finallyethylene was continuously supplied thereto to keep the total pressure inthe autoclave constant at 0.8 MPa. After reacted for 2 hours, the insideof the autoclave was vented to the atmosphere, and the resultant polymerproduct was discharged from the autoclave, and weighed for its weight(by mass) after drying. The particulars of the polymerization reactionwas listed in the following Table I-1.

Example I-3-1

Substantially the same as the Example I-3, except for the followingchanges:

The reaction temperature was kept at 70° C., in the absence of hydrogengas, and the total pressure in the autoclave was kept at 0.5 MPa. Theparticulars of the polymerization reaction was listed in the followingTable I-1.

Example I-3-2

Substantially the same as the Example I-3, except for the followingchanges:

2 minutes after continuously supplying ethylene, 60 g hexene-1 was addedall at once. The particulars of the polymerization reaction was listedin the following Table I-1.

Reference Example I-1-1

Substantially the same as the Example I-1, except for the followingchanges:

The ratio by molar of the magnesium compound to the nonmetalloceneligand was changed to 1:0.008.

The thus obtained catalyst was named as CAT-I-A.

The polymerization was conducted in line with the Example I-3-2.

The particulars of the polymerization reaction was listed in thefollowing Table I-1.

Reference Example I-1-2

Substantially the same as the Example I-1, except for the followingchanges:

The ratio by molar of the magnesium compound to the nonmetalloceneligand was changed to 1:0.002.

The thus obtained catalyst was named as CAT-I-B.

The polymerization was conducted in line with the Example I-3-2.

The particulars of the polymerization reaction was listed in thefollowing Table I-1.

Reference Example I-1-3

Substantially the same as the Example I-1, except for the followingchanges:

No nonmetallocene ligand was used.

The thus obtained catalyst was named as CAT-I-C.

The polymerization was conducted in line with the Example I-3-1 and theExample I-3-2 respectively.

The particulars of the polymerization reaction was listed in thefollowing Table I-1.

Reference Example I-1-4

Substantially the same as the Example I-1, except for the followingchanges:

The modified carrier was not treated by titanium tetrachloride.

The thus obtained catalyst was named as CAT-I-D.

The polymerization was conducted in line with the Example I-3-1 and theExample I-3-2 respectively.

The particulars of the polymerization reaction was listed in thefollowing Table I-1.

TABLE I-1 The results of the olefin polymerization obtained with thesupported nonmetallocene catalysts Content Molecular H₂ Bulk of weightExperiment Catalyst pressure Poly activity density comonomer Mvdistribution No. No. Co-catalyst (MPa) comonomer (kgPE/gCat) (g/cm³)(mol %) (10⁴ g/mol) (Mw/Mn) 1 CAT-I-1 triethylaluminum 0.2 — 74.4 0.337— — 3.23 2 CAT-I-1 triethylaluminum 0 — 111.0 0.328 — 323 3 CAT-I-1triethylaluminum 0.2 1-hexene 87.7 0.341 0.67 — 3.34 4 CAT-I-1methylaluminoxane 0.2 1-hexene 101.3 0.350 1.07 — 2.87 5 CAT-I-1-1triethylaluminum 0.2 — 37.6 0.323 — — 6 CAT-I-1-2 triethylaluminum 0.2 —91.1 0.302 — — 7 CAT-I-1-3 triethylaluminum 0.2 — 63.8 0.297 — 8CAT-I-1-4 triethylaluminum 0.2 — 40.6 0.284 — 9 CAT-I-2 triethylaluminum0.2 — 58.5 0.304 — — 3.11 10 CAT-I-2 triethylaluminum 0 — 123.7 0.319 —436 11 CAT-I-2 triethylaluminum 0.2 1-hexene 79.2 0.325 0.83 — 3.28 12CAT-I-2 methylaluminoxane 0.2 1-hexene 94.4 0.344 1.22 — 2.69 13CAT-I-2-1 triethylaluminum 0.2 — 35.6 0.300 — — 14 CAT-I-2-2triethylaluminum 0.2 — 95.4 0.293 — — 15 CAT-I-2-3 triethylaluminum 0.2— 76.0 0.280 — — 16 CAT-I-2-4 triethylaluminum 0.2 — 47.2 0.275 — — 17CAT-I-A methylaluminoxane 0.2 1-hexene 127.4 0.356 1.24 — 2.62 18CAT-I-B methylaluminoxane 0.2 1-hexene 86.7 0.335 0.86 — 2.93 19 CAT-I-Ctriethylaluminum 0 — 4.42 0.283 — 184 20 CAT-I-C methylaluminoxane 0.21-hexene 52.5 0.252 0.57 — 4.74 21 CAT-I-D triethylaluminum 0 — noactivity — — — —

Upon comparison of the results of the experiment No. 1 and those of theexperiment No. 3, the results of the experiment No. 9 and those of theexperiment No. 11, in the Table I-1, it is clear that the presentcatalyst shows a significant comonomer effect, i.e. the activity incopolymerization is significantly higher than that inhomopolymerization. Further, by the copolymerization, the bulk densityof the polymer can be increased, i.e. the polymer morphology can beimproved. However, there is limited influence on the molecular weightdistribution of the polymer.

Upon comparison of the results of the experiment No. 3 and those of theexperiment No. 4, the results of the experiment No. 11 and those of theexperiment No. 12, it is clear that the activity of the catalyst incopolymerization and the content of the comonomer can be furtherincreased, and the bulk density of the polymer can be further improved,by using MAO as the co-catalyst.

Upon comparison of the results of the experiment Nos. 4, 17 and 18 inthe Table I-1, it is clear that by increasing or reducing the ratio bymolar of the nonmetallocene ligand to the magnesium compound, theactivity in ethylene polymerization of the catalyst and the content ofthe comonomer in the polymer can be increased or decreased, and themolecular weight distribution of the polymer can be somewhat broadenedor narrowed.

Upon comparison of the results of the experiment No. 2 and those of theexperiment No. 19 in the Table I-1, it is clear that if thepolymerization was conducted in the absence of hydrogen gas, thecatalyst CAT-C which contains no nonmetallocene ligand is inferior tothe catalyst CAT-1 which contains a nonmetallocene ligand inpolymerization activity, bulk density and molecular weight.

Upon comparison of the results of the experiment Nos. 1 to 8 and thoseof the experiment Nos. 9 to 16 in the Table I-1, it is clear that thesupported nonmetallocene catalyst obtained by a process wherein themodified carrier was firstly subject to the treatment with an assistantchemical treating agent and then to that with a chemical treating agentshows increased activity and polymer bulk density, somewhat increasedcomonomer content, narrowed polymer molecular weight distribution, ascompared with the supported nonmetallocene catalyst obtained by aprocess wherein the modified carrier is subject only to the treatmentwith a chemical treating agent.

As can be seen from these facts, in the process according to thisinvention, the ligand shows a function of improving catalyst activity,polymer bulk density, and copolymerization performance, and in thepolymerization involving no hydrogen gas, of increasing the molecularweight of the polymer. Therefore, it is possible to freely adjust thepolymerization activity and the copolymerization performance of theresultant supported nonmetallocene catalyst and the molecular weightdistribution of the polymer resulted from the polymerization by alteringthe amount of the nonmetallocene ligand to be used.

As can be seen from the results of the experiment No. 21 in the TableI-1, it is clear that the catalyst containing merely the nonmetalloceneligand shows no polymerization activity, and will be given same afterreacting with the Group IVB metal compound.

Example II Corresponding to the Second Embodiment Example II-1

2.5 g of anhydrous magnesium chloride as the magnesium compound wasweighted, a predetermined amount of butanol and tetrahydrofuran wereadded thereto, after heated to 60° C. to dissolve same, a predeterminedamount of the nonmetallocene ligand was added thereto and then stirredat 60° C. to completely dissolve same. After stirring for 2 hours,hexane (as the precipitating agent) was added thereto to precipitatesame. The resultant solid was then filtered, washed by a solvent forwashing (which is the same as the precipitating agent) for 2 times (byusing the same amount as that of the precipitating agent each time) andthen uniformly heated to 90° C. and vacuum dried, to obtain the modifiedcarrier.

Then, to the modified carrier, 25 ml hexane as the solvent was added,and then titanium tetrachloride as the chemical treating agent wasdropwise added thereto under stirring over a period of 15 minutes. Thereaction continued at 30° C. for 4 hours, then filtered, washed withhexane for 3 times (25 ml each time), and finally vacuum dried to obtainthe supported nonmetallocene catalyst.

The compound represented by

was used as the nonmetallocene ligand.

In this example, the ratio by molar of the magnesium compound to butanolwas 1:0.5, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:200 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.004, theratio by volume of the precipitating agent to the solvent for dissolvingthe magnesium compound was 1:1, and the ratio by molar of the magnesiumcompound to titanium tetrachloride was 1:0.2.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-1.

Example II-1-1

Substantially the same as the Example II-1, except for the followingchanges:

The alcohol was changed to ethanol, the nonmetallocene ligand waschanged to

the precipitating agent was changed to cyclohexane.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:1, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:240 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.006, theratio by volume of the precipitating agent to the solvent for dissolvingthe magnesium compound was 1:0.5, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.5.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-1-1.

Example II-1-2

Substantially the same as the Example II-1, except for the followingchanges:

The alcohol was changed to propanol, the magnesium compound was changedto magnesium bromide (MgBr₂), the nonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed totoluene, the precipitating agent was changed to cycloheptane, and thechemical treating agent was changed to zirconium tetrachloride (ZrCl₄).

The chemical treating agent was dissolved in 25 ml toluene, and then theresultant solution was dropwise added to the modified carrier over aperiod of 15 minutes. Washing was conducted with toluene for 3 times (25ml each time), and then heated to 120° C. and vacuum dried.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:2, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:100 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.003, theratio by volume of the precipitating agent to the solvent for dissolvingthe magnesium compound was 1:2, and the ratio by molar of the magnesiumcompound to the chemical treating agent was 1:1.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-1-2.

Example II-1-3

Substantially the same as the Example II-1, except for the followingchanges:

The alcohol was changed to iso-octanol, the magnesium compound waschanged to ethoxy magnesium chloride (MgCl(OC₂H₅)), the nonmetalloceneligand was changed to

the solvent for dissolving the magnesium compound was changed to ethylbenzene, the precipitating agent was changed to decane, and the chemicaltreating agent was changed to tetraethyl titanium (Ti(CH₃CH₂)₄).

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:0.2, the ratio of the magnesium compound to the solventfor dissolving the magnesium compound was 1 mol:300 ml, the ratio bymolar of the magnesium compound to the nonmetallocene ligand was 1:0.10,the ratio by volume of the precipitating agent to the solvent fordissolving the magnesium compound was 1:0.8, and the ratio by molar ofthe magnesium compound to the chemical treating agent was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-1-3.

Example II-1-4

Substantially the same as the Example II-1, except for the followingchanges:

The alcohol was changed to pentanol, the magnesium compound was changedto ethyl magnesium (Mg(C₂H₅)₂), the nonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed to xylene,and the chemical treating agent was changed to triisobutyl chlorotitanium (TiCl(i-C₄H₉)₃).

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:3, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:350 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.001, theratio by volume of the precipitating agent to the solvent for dissolvingthe magnesium compound was 1:0.25, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.30.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-1-4.

Example II-1-5

Substantially the same as the Example II-1, except for the followingchanges:

The magnesium compound was changed to ethoxy magnesium (Mg(OC₂H₅)₂), thenonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed top-chloro toluene, and the chemical treating agent was changed totetraethoxy titanium (Ti(OCH₃CH₂)₄).

Example II-1-6

Substantially the same as the Example II-1, except for the followingchanges:

The magnesium compound was changed to isobutyl magnesium (Mg(i-C₄H₉)₂),the nonmetallocene ligand was changed to

Example II-2

2.5 g of anhydrous magnesium chloride as the magnesium compound wasweighted, a predetermined amount of butanol and tetrahydrofuran wereadded thereto, after heated to 60° C. to dissolve same, a predeterminedamount of the nonmetallocene ligand was added thereto and then stirredat 60° C. to completely dissolve same. After stirring for 2 hours,hexane (as the precipitating agent) was added thereto to precipitatesame. The resultant solid was then filtered, washed by a solvent forwashing (which is the same as the precipitating agent) for 2 times (byusing the same amount as that of the precipitating agent each time) andthen uniformly heated to 90° C. and vacuum dried, to obtain the modifiedcarrier.

Then, to the modified carrier, 25 ml hexane was added, and then triethylaluminum as the assistant chemical treating agent was dropwise addedthereto under stirring over a period of 15 minutes. The reactioncontinued under stirring for 1 hour, then filtered, washed with hexanefor 2 times (25 ml each time). Then, 25 ml hexane was added thereto, andthen titanium tetrachloride as the chemical treating agent was dropwiseadded thereto over a period of 15 minutes. The reaction continued at 60°C. for 4 hours, then filtered, washed with hexane for 3 times (25 mleach time), and finally vacuum dried to obtain the supportednonmetallocene catalyst.

The compound represented by

was used as the nonmetallocene ligand.

In this example, the ratio by molar of the magnesium compound to butanolwas 1:0.5, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:200 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.004, theratio by volume of the precipitating agent to the solvent for dissolvingthe magnesium compound was 1:1, the ratio by molar of the magnesiumcompound to the assistant chemical treating agent was 1:0.35, and theratio by molar of the magnesium compound to titanium tetrachloride was1:0.2.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-2.

Example II-2-1

Substantially the same as the Example II-2, except for the followingchanges:

The alcohol was changed to ethanol, the nonmetallocene ligand waschanged to

the precipitating agent was changed to cyclohexane, the assistantchemical treating agent was changed to methyl aluminoxane.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:1, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:240 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.006, theratio by volume of the precipitating agent to the solvent for dissolvingthe magnesium compound was 1:0.5, the ratio by molar of the magnesiumcompound to the assistant chemical treating agent was 1:0.5, and theratio by molar of the magnesium compound to the chemical treating agentwas 1:0.5.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-2-1.

Example II-2-2

Substantially the same as the Example II-2, except for the followingchanges:

The alcohol was changed to propanol, the magnesium compound was changedto magnesium bromide (MgBr₂), the nonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed totoluene, the precipitating agent was changed to cycloheptane, theassistant chemical treating agent was changed to isobutyl aluminoxane,the chemical treating agent was changed to zirconium tetrachloride(ZrCl₄).

The chemical treating agent was dissolved in 25 ml toluene, and then theresultant solution was dropwise added to the modified carrier over aperiod of 15 minutes. Washing was conducted with toluene for 3 times (25ml each time), and then heated to 120° C. and vacuum dried.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:2, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:100 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.003, theratio by volume of the precipitating agent to the solvent for dissolvingthe magnesium compound was 1:2, the ratio by molar of the magnesiumcompound to the assistant chemical treating agent was 1:0.4, and theratio by molar of the magnesium compound to the chemical treating agentwas 1:1.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-2-2.

Example II-2-3

Substantially the same as the Example II-2, except for the followingchanges:

The alcohol was changed to iso-octanol, the magnesium compound waschanged to ethoxy magnesium chloride (MgCl(OC₂H₅)), the nonmetalloceneligand was changed to

the solvent for dissolving the magnesium compound was changed to ethylbenzene, the precipitating agent was changed to decane, the assistantchemical treating agent was changed to triisobutyl aluminum, and thechemical treating agent was changed to tetraethyl titanium(Ti(CH₃CH₂)₄).

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:0.2, the ratio of the magnesium compound to the solventfor dissolving the magnesium compound was 1 mol:300 ml, the ratio bymolar of the magnesium compound to the nonmetallocene ligand was 1:0.10,the ratio by volume of the precipitating agent to the solvent fordissolving the magnesium compound was 1:0.8, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:1.0,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-2-3.

Example II-2-4

Substantially the same as the Example II-2, except for the followingchanges:

The alcohol was changed to pentanol, the magnesium compound was changedto ethyl magnesium (Mg(C₂H₅)₂), the nonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed to xylene,the assistant chemical treating agent was changed to trimethyl aluminum,and the chemical treating agent was changed to triisobutyl chlorotitanium (TiCl(i-C₄H₉)₃).

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:3, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:350 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.001, theratio by volume of the precipitating agent to the solvent for dissolvingthe magnesium compound was 1:0.25, the ratio by molar of the magnesiumcompound to the assistant chemical treating agent was 1:0.20, and theratio by molar of the magnesium compound to the chemical treating agentwas 1:0.30.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-2-4.

Example II-2-5

Substantially the same as the Example II-2, except for the followingchanges:

The magnesium compound was changed to ethoxy magnesium (Mg(OC₂H₅)₂), thenonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed top-chloro toluene, and the chemical treating agent was changed totetraethoxy titanium (Ti(OCH₃CH₂)₄).

Example II-2-6

Substantially the same as the Example II-2, except for the followingchanges:

The magnesium compound was changed to isobutyl magnesium (Mg(i-C₄H₉)₂),the nonmetallocene ligand was changed to

Reference Example II-1-A

Substantially the same as the Example II-1, except for the followingchanges:

No nonmetallocene ligand was used.

The thus obtained catalyst was named as CAT-II-1-A.

Reference Example II-1-B

Substantially the same as the Example II-1, except for the followingchanges:

The ratio by molar of the magnesium compound to the nonmetalloceneligand was changed to 1:0.008.

The thus obtained catalyst was named as CAT-II-1-B.

Reference Example II-1-C

Substantially the same as the Example II-1, except for the followingchanges:

The ratio by molar of the magnesium compound to the nonmetalloceneligand was changed to 1:0.002.

The thus obtained catalyst was named as CAT-II-1-C.

Reference Example II-1-D

Substantially the same as the Example II-1, except for the followingchanges:

The modified carrier was not treated by titanium tetrachloride.

The thus obtained catalyst was named as CAT-II-1-D.

Reference Example II-1-E

Substantially the same as the Example II-1, except for the followingchanges:

The modified carrier was not subjected to the treatment of theprecipitating agent, but was obtained by directly vacuum dried at 90° C.

The thus obtained catalyst was named as CAT-II-1-E.

Example II-3 Application Example II

The catalysts CAT-II-1, CAT-II-2, CAT-II-1-1 to CAT-II-1-4, CAT-II-2-1to CAT-II-2-4, CAT-II-1-A to CAT-II-1-E were respectively weighted, andused in combination with a co-catalyst (methyl aluminoxane or triethylaluminum), for ethylene homopolymerization/copolymerization and ultrahigh molecular weight polyethylene preparation under the followingconditions according to the following processes respectively.

Homopolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 0.8 MPa, a polymerization temperature of 85°C., a partial pressure of hydrogen gas of 0.2 MPa, a polymerization timeof 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 20 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and then hydrogen gas was supplied thereto till 0.2 MPa,and finally ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 0.8 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table II-1.

Copolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 0.8 MPa, a polymerization temperature of 85°C., a partial pressure of hydrogen gas of 0.2 MPa, a polymerization timeof 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 20 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto. Hexene-1 (50 g) was added thereto all at once as thecomonomer, and then hydrogen gas was supplied thereto till 0.2 MPa, andfinally ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 0.8 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table II-1.

Preparation of ultra high molecular weight polyethylene: an autoclavefor polymerization (5 L), a slurry polymerization process, hexane (2.5L) as the solvent, a total polymerization pressure of 0.5 MPa, apolymerization temperature of 70° C., a ratio by molar of theco-catalyst to the active metal in the catalyst of 100, a polymerizationtime of 6 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 20 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and finally ethylene was continuously supplied thereto tokeep the total polymerization pressure constant at 0.5 MPa. Uponcompletion of the polymerization, the inside of the autoclave was ventedto the atmosphere, and the resultant polymer product was discharged fromthe autoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table II-2.

TABLE II-1 The results of the olefin polymerization obtained with thesupported nonmetallocene catalysts ratio by molar of co-catalystMolecular Experiment to active Poly activity Bulk density weight No.Catalyst No. Co-catalyst metal type (kgPE/gCat) (g/cm³) distribution 1CAT-II-1 triethylaluminum 100 homopolymerization 63.7 0.34 3.10 2CAT-II-1 methylaluminoxane 100 homopolymerization 72.5 0.35 2.64 3CAT-II-1 triethylaluminum 100 copolymerization 80.1 0.35 3.35 4 CAT-II-1triethylaluminum 500 copolymerization 82.4 0.35 3.22 5 CAT-II-1-1triethylaluminum 100 homopolymerization 83.8 0.34 — 6 CAT-II-1-2triethylaluminum 100 homopolymerization 60.4 0.33 — 7 CAT-II-1-3triethylaluminum 100 homopolymerization 74.7 0.33 — 8 CAT-II-1-4triethylaluminum 100 homopolymerization 55.9 0.33 — 9 CAT-II-2triethylaluminum 100 homopolymerization 70.5 0.34 3.02 10 CAT-II-2methylaluminoxane 100 homopolymerization 78.4 0.35 2.59 11 CAT-II-2triethylaluminum 100 copolymerization 90.2 0.35 3.17 12 CAT-II-2-1triethylaluminum 100 homopolymerization 87.6 0.35 — 13 CAT-II-2-2triethylaluminum 100 homopolymerization 65.9 0.34 — 14 CAT-II-2-3triethylaluminum 100 homopolymerization 80.3 0.33 — 15 CAT-II-2-4triethylaluminum 100 homopolymerization 60.1 0.33 — 16 CAT-II-1-Atriethylaluminum 100 homopolymerization 44.6 0.28 4.83 17 CAT-II-1-Btriethylaluminum 100 homopolymerization 70.9 0.34 2.77 18 CAT-II-1-Ctriethylaluminum 100 homopolymerization 58.5 0.32 3.45 19 CAT-II-1-Dtriethylaluminum 100 homopolymerization no activity — — 20 CAT-II-1-Etriethylaluminum 100 homopolymerization 72.5 0.31 3.04

TABLE II-2 The results of the ultra high molecular weight polyethylenepreparation obtained with the supported nonmetallocene catalysts Polyactivity Bulk Mv Experiment (kgPE/ density (10⁴ No. Catalyst No.Co-catalyst gCat) (g/cm³) g/mol) 1 CAT-II-1 triethyl 80.4 0.37 446aluminum 2 CAT-II-1 methyl 78.3 0.39 482 aluminoxane 3 CAT-II-2 triethyl85.6 0.38 475 aluminum 4 CAT-II-2 methyl 81.7 0.40 550 aluminoxane 5CAT-II-1-A triethyl 56.9 0.35 314 aluminum 6 CAT-II-1-B triethyl 92.60.36 540 aluminum 7 CAT-II-1-C triethyl 62.7 0.36 365 aluminum 8CAT-II-1-D triethyl no activity — — aluminum 9 CAT-II-1-E triethyl 91.60.35 432 aluminum

Upon comparison of the results of the experiment No. 1 and those of theexperiment No. 3, the results of the experiment No. 10 and those of theexperiment No. 11, in the Table II-1, it is clear that the presentcatalyst shows a significant comonomer effect, i.e. the activity incopolymerization is higher than that in homopolymerization. Further, bythe copolymerization, the bulk density of the polymer can be increased,i.e. the polymer morphology can be improved. However, there is limitedinfluence on the molecular weight distribution of the polymer.

Upon comparison of the results of the experiment No. 1 and those of theexperiment No. 2, the results of the experiment No. 9 and those of theexperiment No. 10, it is clear that the activity of the catalyst inpolymerization in the presence of hydrogen gas can be further increased,the bulk density of the polymer can be further improved, and themolecular weight distribution of the polymer can be further narrowed, ifusing MAO as the co-catalyst.

Upon comparison of the results of the experiment Nos. 1, 17 and 18 inthe Table II-1, it is clear that by increasing or reducing the ratio bymolar of the nonmetallocene ligand to the magnesium compound, theactivity for ethylene polymerization of the catalyst was increased ordecreased, and the molecular weight distribution of the polymer wassomewhat narrowed or broadened. This effect was further supported by acomparison of the results of the experiment Nos. 16 and 1, i.e. noaddition of the nonmetallocene ligand will lower the activity of thecatalyst and broaden the molecular weight distribution of the polymer.

Upon comparison of the results of the experiment Nos. 1 to 8 and thoseof the experiment Nos. 9 to 15 in the Table II-1, it is clear that thesupported nonmetallocene catalyst obtained by a process wherein themodified carrier was firstly subject to the treatment with an assistantchemical treating agent and then to that with a chemical treating agentshows increased catalyst activity and polymer bulk density, and narrowedpolymer molecular weight distribution, as compared with the supportednonmetallocene catalyst obtained by a process wherein the modifiedcarrier is subject only to the treatment with a chemical treating agent.

As can be seen from the Table II-2, it is possible to prepare an ultrahigh molecular weight polyethylene (with to some degree increased bulkdensity) by using the catalyst according to this invention. Uponcomparison of the results from the experiment No. 1 and those from theexperiment No. 2, the results from the experiment No. 3 and those fromthe experiment No. 4, it is clear that the viscosity averaged molecularweight of the polymer can be increased by using MAO as the co-catalyst.Upon comparison of the results from the experiment No. 1 and those fromthe reference example experiment Nos. 5 to 8 in the Table II-2, it isclear that the viscosity averaged molecular weight of the polymerincreases or decreases as the amount of the nonmetallocene ligand to beintroduced into the catalyst increases or decreases. This fact indicatesthat the nonmetallocene ligand further shows a function of increasingthe viscosity averaged molecular weight of the polymer.

Upon comparison of the results of the experiment No. 1 and those of theexperiment No. 14 in the Table II-1, or the results of the experimentNo. 1 and those of the experiment No. 9 in the Table II-2, it is clearthat the polymer produced by using the catalyst obtained in line withthe present process shows a higher bulk density than that produced byusing a catalyst obtained by a directly drying process.

As can be seen from the results of the experiment No. 19 in the TableII-1 and the results of the experiment No. 8 in the Table II-2, it isclear that the catalyst containing merely the nonmetallocene ligandshows no polymerization activity, and will be given same after reactingwith the Group IVB metal compound.

Example III Corresponding to the Third Embodiment Example III-1

Anhydrous magnesium chloride was used as the magnesium compound, butanolwas used as the alcohol, tetrahydrofuran was used as the solvent fordissolving the magnesium compound, titanium tetrachloride was used asthe chemical treating agent, silica gel (ES757, from the Ineos Company)was used as the porous carrier, the compound represented by

was used as the nonmetallocene ligand.

The silica gel was thermally activated by continuously calcinating at600° C. under a N₂ atmosphere for 4 hours before use.

2.5 g of anhydrous magnesium chloride as the magnesium compound wasweighted, a predetermined amount of butanol and tetrahydrofuran wereadded thereto, after heated to 60° C. to dissolve same, a predeterminedamount of the nonmetallocene ligand was added thereto and continuouslystirred at 60° C. to completely dissolve same. Then, the thermallyactivated silica gel was added thereto to form a slurry. After stirringfor 2 hours, the resultant was uniformly heated to 90° C. and directlyvacuum dried, to obtain the composite carrier.

Then, to the modified carrier, 25 ml hexane as the solvent was added,and then titanium tetrachloride as the chemical treating agent wasdropwise added thereto under stirring over a period of 15 minutes. Thereaction continued at 30° C. for 4 hours, then filtered, washed withhexane for 3 times (25 ml each time), and finally vacuum dried to obtainthe supported nonmetallocene catalyst.

In this example, the ratio by molar of the magnesium compound to butanolwas 1:0.5, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:200 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.004, theratio by weight of the magnesium compound to the porous carrier was 1:2,and the ratio by molar of the magnesium compound to titaniumtetrachloride was 1:0.2.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1.

Example III-1-1

Substantially the same as the Example III-1, except for the followingchanges:

The alcohol was changed to ethanol, the porous carrier was changed tosilica gel (955, from the Grace Company), which has been thermallyactivated by continuously calcinating at 400° C. under a N₂ gasatmosphere for 8 hours.

The nonmetallocene ligand was changed to

The slurry was vacuum dried at 80° C.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:1, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:240 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.006, theratio by weight of the magnesium compound to the porous carrier was 1:1,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.5.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-1.

Example III-1-2

Substantially the same as the Example III-1, except for the followingchanges:

The porous carrier was changed to Al₂C₃, which has been thermallyactivated by continuously calcinating at 700° C. under a N₂ gasatmosphere for 6 hours.

The alcohol was changed to propanol, the magnesium compound was changedto magnesium bromide (MgBr₂), the nonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed totoluene, and the chemical treating agent was changed to zirconiumtetrachloride (ZrCl₄).

The slurry was vacuum dried at 100° C.

The chemical treating agent was dissolved in 25 ml toluene, and then theresultant solution was dropwise added to the composite carrier over aperiod of 15 minutes. Washing was conducted with toluene for 3 times (25ml each time), and then heated to 120° C. and vacuum dried.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:2, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:100 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.003, theratio by weight of the magnesium compound to the porous carrier was 1:3,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:1.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-2.

Example III-1-3

Substantially the same as the Example III-1, except for the followingchanges:

The porous carrier was changed to montmorillonite, which has beenthermally activated by continuously calcinating at 400° C. under a N₂gas atmosphere for 8 hours.

The alcohol was changed to iso-octanol, the magnesium compound waschanged to ethoxy magnesium chloride (MgCl(OC₂H₅)), the nonmetalloceneligand was changed to

the solvent for dissolving the magnesium compound was changed to ethylbenzene, and the chemical treating agent was changed to tetraethyltitanium (Ti(CH₃CH₂)₄).

The slurry was dried at 130° C. under a N₂ purge.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:0.25, the ratio of the magnesium compound to the solventfor dissolving the magnesium compound was 1 mol:300 ml, the ratio bymolar of the magnesium compound to the nonmetallocene ligand was1:0.010, the ratio by weight of the magnesium compound to the porouscarrier was 1:0.5, and the ratio by molar of the magnesium compound tothe chemical treating agent was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-3.

Example III-1-4

Substantially the same as the Example III-1, except for the followingchanges:

The porous carrier was changed to polystyrene, which has been thermallyactivated by continuously drying at 100° C. under a N₂ gas atmospherefor 12 hours.

The alcohol was changed to pentanol, the magnesium compound was changedto ethyl magnesium (Mg(C₂H₅)₂), the nonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed to xylene,and the chemical treating agent was changed to triisobutyl chlorotitanium (TiCl(i-C₄H₉)₃).

The slurry was vacuum dried at 60° C.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:3, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:350 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.001, theratio by weight of the magnesium compound to the porous carrier was1:10, and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.3.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-4.

Example III-1-5

Substantially the same as the Example III-1, except for the followingchanges:

The porous carrier was changed to kieselguhr, which has been thermallyactivated by continuously calcinating at 500° C. under a N₂ gasatmosphere for 8 hours.

The magnesium compound was changed to ethoxy magnesium (Mg(OC₂H₅)₂), thenonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed top-chloro toluene, and the chemical treating agent was changed totetraethoxy titanium (Ti(OCH₃CH₂)₄).

Example III-1-6

Substantially the same as the Example III-1, except for the followingchanges:

The magnesium compound was changed to isobutyl magnesium (Mg(i-C₄H₉)₂),the nonmetallocene ligand was changed to

The porous carrier was changed to a mixed oxide of silica and MgO (at aratio by weight of 1:1), which has been thermally activated bycontinuously calcinating at 600° C. under an Ar gas atmosphere for 4hours.

Example III-2

Anhydrous magnesium chloride was used as the magnesium compound, butanolwas used as the alcohol, tetrahydrofuran was used as the solvent fordissolving the magnesium compound, titanium tetrachloride was used asthe chemical treating agent, silica gel (ES757, from the Ineos Company)was used as the porous carrier, the compound represented by

was used as the nonmetallocene ligand.

The silica gel was thermally activated by continuously calcinating at600° C. under a N₂ atmosphere for 4 hours before use.

2.5 g of anhydrous magnesium chloride as the magnesium compound wasweighted, a predetermined amount of butanol and tetrahydrofuran wereadded thereto, after heated to 60° C. to dissolve same, a predeterminedamount of the nonmetallocene ligand was added thereto and continuouslystirred at 60° C. to completely dissolve same. Then, the thermallyactivated silica gel was added thereto to form a slurry. After stirringfor 2 hours, the resultant was uniformly heated to 90° C. and directlyvacuum dried, to obtain the composite carrier.

Then, to the composite carrier, 25 ml hexane was added, and thentriethyl aluminum as the assistant chemical treating agent was dropwiseadded thereto under stirring over a period of 15 minutes. The reactioncontinued under stirring for 1 hour, then filtered, washed with hexanefor 2 times (25 ml each time). Then, 25 ml hexane was added thereto, andthen titanium tetrachloride was dropwise added thereto over a period of15 minutes. The reaction continued at 60° C. for 4 hours, then filtered,washed with hexane for 3 times (25 ml each time), and finally vacuumdried to obtain the supported nonmetallocene catalyst.

In this example, the ratio by molar of the magnesium compound to butanolwas 1:0.5, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:200 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.004, theratio by weight of the magnesium compound to the porous carrier was 1:2,the ratio by molar of the magnesium compound to the assistant chemicaltreating agent was 1:0.35, and the ratio by molar of the magnesiumcompound to titanium tetrachloride was 1:0.2.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2.

Example III-2-1

Substantially the same as the Example III-2, except for the followingchanges:

The alcohol was changed to ethanol, the porous carrier was changed tosilica gel (955, from the Grace Company), which has been thermallyactivated by continuously calcinating at 400° C. under a N₂ gasatmosphere for 8 hours.

The nonmetallocene ligand was changed to

the assistant chemical treating agent was changed to methyl aluminoxane.

The slurry was vacuum dried at 80° C.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:1, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:240 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.006, theratio by weight of the magnesium compound to the porous carrier was 1:1,the ratio by molar of the magnesium compound to the assistant chemicaltreating agent was 1:0.5, and the ratio by molar of the magnesiumcompound to the chemical treating agent was 1:0.5.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2-1.

Example III-2-2

Substantially the same as the Example III-2, except for the followingchanges:

The porous carrier was changed to Al₂O₃, which has been thermallyactivated by continuously calcinating at 700° C. under a N₂ gasatmosphere for 6 hours.

The alcohol was changed to propanol, the magnesium compound was changedto magnesium bromide (MgBr₂), the nonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed totoluene, the assistant chemical treating agent was changed to isobutylaluminoxane, and the chemical treating agent was changed to zirconiumtetrachloride (ZrCl₄).

The slurry was vacuum dried at 100° C.

The chemical treating agent was dissolved in 25 ml toluene, and then theresultant solution was dropwise added to the composite carrier over aperiod of 15 minutes. Washing was conducted with toluene for 3 times (25ml each time), and then heated to 120° C. and vacuum dried.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:2, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:100 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.003, theratio by weight of the magnesium compound to the porous carrier was 1:3,the ratio by molar of the magnesium compound to the assistant chemicaltreating agent was 1:0.6, and the ratio by molar of the magnesiumcompound to the chemical treating agent was 1:1.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2-2.

Example III-2-3

Substantially the same as the Example III-2, except for the followingchanges:

The porous carrier was changed to montmorillonite, which has beenthermally activated by continuously calcinating at 400° C. under a N₂gas atmosphere for 8 hours.

The alcohol was changed to iso-octanol, the magnesium compound waschanged to ethoxy magnesium chloride (MgCl(OC₂H₅)), the nonmetalloceneligand was changed to

the solvent for dissolving the magnesium compound was changed to ethylbenzene, the assistant chemical treating agent was changed totriisobutyl aluminum, and the chemical treating agent was changed totetraethyl titanium (Ti(CH₃CH₂)₄).

The slurry was dried at 130° C. under a N₂ purge.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:0.25, the ratio of the magnesium compound to the solventfor dissolving the magnesium compound was 1 mol:300 ml, the ratio bymolar of the magnesium compound to the nonmetallocene ligand was1:0.010, the ratio by weight of the magnesium compound to the porouscarrier was 1:0.5, the ratio by molar of the magnesium compound to theassistant chemical treating agent was 1:1.0, and the ratio by molar ofthe magnesium compound to the chemical treating agent was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2-3.

Example III-2-4

Substantially the same as the Example III-2, except for the followingchanges:

The porous carrier was changed to polystyrene, which has been thermallyactivated by continuously drying at 100° C. under a N₂ gas atmospherefor 12 hours.

The alcohol was changed to pentanol, the magnesium compound was changedto ethyl magnesium (Mg(C₂H₅)₂), the nonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed to xylene,the assistant chemical treating agent was changed to trimethyl aluminum,and the chemical treating agent was changed to triisobutyl chlorotitanium (TiCl(i-C₄H₉)₃).

The slurry was vacuum dried at 60° C.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:3, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:350 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.001, theratio by weight of the magnesium compound to the porous carrier was1:10, the ratio by molar of the magnesium compound to the assistantchemical treating agent was 1:0.75, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.3.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2-4.

Example III-2-5

Substantially the same as the Example III-2, except for the followingchanges:

The porous carrier was changed to kieselguhr, which has been thermallyactivated by continuously calcinating at 500° C. under a N₂ gasatmosphere for 8 hours.

The magnesium compound was changed to ethoxy magnesium (Mg(OC₂H₅)₂), thenonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed top-chloro toluene, and the chemical treating agent was changed totetraethoxy titanium (Ti(OCH₃CH₂)₄).

Example III-2-6

Substantially the same as the Example III-2, except for the followingchanges:

The magnesium compound was changed to isobutyl magnesium (Mg(i-C₄H₉)₂),the nonmetallocene ligand was changed to

The porous carrier was changed to a mixed oxide of silica and MgO (at aratio by weight of 1:1), which has been thermally activated bycontinuously calcinating at 600° C. under an Ar gas atmosphere for 4hours.

Reference Example III-1-A

Substantially the same as the Example III-1, except for the followingchanges:

No nonmetallocene ligand was used.

The thus obtained catalyst was named as CAT-III-1-A.

Reference Example III-1-B

Substantially the same as the Example III-1, except for the followingchanges:

The ratio by molar of the magnesium compound to the nonmetalloceneligand was changed to 1:0.008.

The thus obtained catalyst was named as CAT-III-1-B.

Reference Example III-1-C

Substantially the same as the Example III-1, except for the followingchanges:

The ratio by molar of the magnesium compound to the nonmetalloceneligand was changed to 1:0.002.

The thus obtained catalyst was named as CAT-III-1-C.

Reference Example III-1-D

Substantially the same as the Example III-1, except for the followingchanges:

The composite carrier was not treated by titanium tetrachloride.

The thus obtained catalyst was named as CAT-III-1-D.

Reference Example III-1-E

Substantially the same as the Example III-1, except for the followingchanges:

60 ml hexane was added to the slurry to precipitate same, which was thenfiltered, washed with hexane for 3 times (60 ml per time), and finallyvacuum dried at 90° C.

The thus obtained catalyst was named as CAT-III-1-E.

Example III-3 Application Example III

The catalysts CAT-III-1, CAT-III-2, CAT-III-1-1 to CAT-III-1-4,CAT-III-2-1 to CAT-III-2-4, CAT-III-1-A to CAT-III-1-E were respectivelyweighted, and used in combination of a co-catalyst (methyl aluminoxaneor triethyl aluminum), for ethylene homopolymerization/copolymerizationand ultra high molecular weight polyethylene preparation under thefollowing conditions according to the following processes respectively.

Homopolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 0.8 MPa, a polymerization temperature of 85°C., a partial pressure of hydrogen gas of 0.2 MPa, a polymerization timeof 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 20 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and then hydrogen gas was supplied thereto till 0.2 MPa,and finally ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 0.8 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table III-1.

Copolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 0.8 MPa, a polymerization temperature of 85°C., a partial pressure of hydrogen gas of 0.2 MPa, a polymerization timeof 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 20 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto. Hexene-1 (50 g) was added thereto all at once as thecomonomer, and then hydrogen gas was supplied thereto till 0.2 MPa, andfinally ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 0.8 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table III-1.

Preparation of ultra high molecular weight polyethylene: an autoclavefor polymerization (5 L), a slurry polymerization process, hexane (2.5L) as the solvent, a total polymerization pressure of 0.5 MPa, apolymerization temperature of 70° C., a ratio by molar of theco-catalyst to the active metal in the catalyst of 100, a polymerizationtime of 6 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 20 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and finally ethylene was continuously supplied thereto tokeep the total polymerization pressure constant at 0.5 MPa. Uponcompletion of the polymerization, the inside of the autoclave was ventedto the atmosphere, and the resultant polymer product was discharged fromthe autoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table III-2.

TABLE III-1 The results of the olefin polymerization obtained with thesupported nonmetallocene catalysts ratio by molar of co-catalystMolecular Experiment to active Poly activity Bulk density weight No.Catalyst No. Co-catalyst metal type (kgPE/gCat) (g/cm³) distribution 1CAT-III-1 triethylaluminum 100 homopolymerization 8.2 0.34 2.98 2CAT-III-1 methylaluminoxane 100 homopolymerization 8.9 0.36 2.61 3CAT-III-1 triethylaluminum 100 copolymerization 9.7 0.36 3.25 4CAT-III-1 triethylaluminum 500 copolymerization 10.1 0.36 3.10 5CAT-III-1-1 triethylaluminum 100 homopolymerization 10.3 0.35 — 6CAT-III-1-2 triethylaluminum 100 homopolymerization 7.8 0.34 — 7CAT-III-1-3 triethylaluminum 100 homopolymerization 9.6 0.34 — 8CAT-III-1-4 triethylaluminum 100 homopolymerization 7.3 0.34 — 9CAT-III-2 triethylaluminum 100 homopolymerization 9.0 0.35 3.00 10CAT-III-2 methylaluminoxane 100 homopolymerization 10.0 0.36 2.55 11CAT-III-2 triethylaluminum 100 copolymerization 11.1 0.36 3.13 12CAT-III-2-1 triethylaluminum 100 homopolymerization 10.8 0.36 — 13CAT-III-2-2 triethylaluminum 100 homopolymerization 8.5 0.35 — 14CAT-III-2-3 triethylaluminum 100 homopolymerization 9.9 0.34 — 15CAT-III-2-4 triethylaluminum 100 homopolymerization 7.7 0.34 — 16CAT-III-1-A triethylaluminum 100 homopolymerization 5.8 0.29 4.74 17CAT-III-1-B triethylaluminum 100 homopolymerization 9.1 0.35 2.73 18CAT-III-1-C triethylaluminum 100 homopolymerization 7.6 0.33 3.40 19CAT-III-1-D triethylaluminum 100 homopolymerization no activity — — 20CAT-III-1-E triethylaluminum 100 homopolymerization 7.2 0.37 3.04

TABLE III-2 The results of the ultra high molecular weight polyethylenepreparation obtained with the supported nonmetallocene catalysts Polyactivity Bulk Mv Experiment (kgPE/ density (10⁴ No. Catalyst No.Co-catalyst gCat) (g/cm³) g/mol) 1 CAT-III-1 triethyl 11.1 0.38 450aluminum 2 CAT-III-1 methyl 10.5 0.40 475 aluminoxane 3 CAT-III-2triethyl 11.8 0.39 460 aluminum 4 CAT-III-2 methyl 11.2 0.39 560aluminoxane 5 CAT-III-1-A triethyl 7.8 0.36 210 aluminum 6 CAT-III-1-Btriethyl 12.7 0.37 550 aluminum 7 CAT-III-1-C triethyl 8.5 0.37 370aluminum 8 CAT-III-1-D triethyl no activity — — aluminum 9 CAT-III-1-Etriethyl 9.8 0.40 430 aluminum

Upon comparison of the results of the experiment No. 1 and those of theexperiment No. 3, the results of the experiment No. 10 and those of theexperiment No. 11, in the Table III-1, it is clear that the presentcatalyst shows a significant comonomer effect, i.e. the activity incopolymerization is higher than that in homopolymerization. Further, bythe copolymerization, the bulk density of the polymer can be increased,i.e. the polymer morphology can be improved. However, there is limitedinfluence on the molecular weight distribution of the polymer.

Upon comparison of the results of the experiment No. 1 and those of theexperiment No. 2, the results of the experiment No. 9 and those of theexperiment No. 10, it is clear that the activity of the catalyst forpolymerization in the presence of hydrogen gas can be further increased,the bulk density of the polymer can be further improved, and themolecular weight distribution of the polymer can be further narrowed, ifusing MAO as the co-catalyst.

Upon comparison of the results of the experiment Nos. 1, 17 and 18 inthe Table III-1, it is clear that by increasing or reducing the ratio bymolar of the nonmetallocene ligand to the magnesium compound, theactivity for ethylene polymerization of the catalyst was increased ordecreased, and the molecular weight distribution of the polymer wassomewhat narrowed or broadened. This effect was further supported by acomparison of the results of the experiment Nos. 16 and 1, i.e. noaddition of the nonmetallocene ligand will lower the activity of thecatalyst and broaden the molecular weight distribution of the polymer.

Upon comparison of the results of the experiment Nos. 1 to 8 and thoseof the experiment Nos. 9 to 15 in the Table III-1, or the results of theexperiment Nos. 1 to 2 and those of the experiment Nos. 3 to 4 in theTable III-2, it is clear that the supported nonmetallocene catalystobtained by a process wherein the composite carrier was firstly subjectto the treatment with an assistant chemical treating agent and then tothat with a chemical treating agent shows increased catalyst activityand polymer bulk density, narrowed polymer molecular weight distributionand increased viscosity averaged molecular weight of the ultra highmolecular weight polyethylene, as compared with the supportednonmetallocene catalyst obtained by a process wherein the compositecarrier is subject only to the treatment with a chemical treating agent.

As can be seen from the Table III-2, it is possible to prepare an ultrahigh molecular weight polyethylene (with to some degree increased bulkdensity) by using the catalyst according to this invention. Uponcomparison of the results from the experiment No. 1 and those from theexperiment No. 2, the results from the experiment No. 3 and those fromthe experiment No. 4, it is clear that the viscosity averaged molecularweight of the polymer can be increased by using MAO as the co-catalyst.Upon comparison of the results from the experiment No. 1 and those fromthe reference example experiment Nos. 5 to 8 in the Table III-2, it isclear that the viscosity averaged molecular weight of the polymerincreases or decreases as the amount of the nonmetallocene ligand to beintroduced into the catalyst increases or decreases. This fact indicatesthat the nonmetallocene ligand further shows a function of increasingthe viscosity averaged molecular weight of the polymer.

As can be seen from the results of the experiment No. 19 in the TableIII-1 and the results of the experiment No. 8 in the Table III-2, it isclear that the catalyst containing merely the nonmetallocene ligandshows no polymerization activity, and will be given same after reactingwith the Group IVB metal compound.

Upon comparison of the results of the experiment Nos. 1 and 14 in theTable III-1, and the results of the experiment Nos. 1 and 9 in the TableIII-2, it is clear that the catalyst obtained by a directly dryingprocess exhibits a higher activity in polymerization than that obtainedby a filtering, washing and drying process.

Example IV Corresponding to the Fourth Embodiment Example IV-1

Anhydrous magnesium chloride was used as the magnesium compound, butanolwas used as the alcohol, tetrahydrofuran was used as the solvent fordissolving the magnesium compound, titanium tetrachloride was used asthe chemical treating agent, silica gel (ES757, from the Ineos Company)was used as the porous carrier, hexane was used as the precipitatingagent, the compound represented by

was used as the nonmetallocene ligand.

The silica gel was thermally activated by continuously calcinating at600° C. under a N₂ atmosphere for 4 hours before use.

2.5 g of anhydrous magnesium chloride as the magnesium compound wasweighted, a predetermined amount of butanol and tetrahydrofuran wereadded thereto, after heated to 60° C. to dissolve same, a predeterminedamount of the nonmetallocene ligand was added thereto and continuouslystirred at 60° C. to completely dissolve same. Then, the thermallyactivated silica gel was added thereto to form a slurry. After stirringfor 2 hours, hexane (as the precipitating agent) was added thereto toprecipitate same. The resultant solid was then filtered, washed by asolvent for washing (which is the same as the precipitating agent) for 2times (by using the same amount as that of the precipitating agent eachtime) and then uniformly heated to 90° C. and vacuum dried, to obtainthe composite carrier.

Then, to the modified carrier, 25 ml hexane as the solvent was added,and then titanium tetrachloride as the chemical treating agent wasdropwise added thereto under stirring over a period of 15 minutes. Thereaction continued at 30° C. for 4 hours, then filtered, washed withhexane for 3 times (25 ml each time), and finally vacuum dried to obtainthe supported nonmetallocene catalyst.

In this example, the ratio by molar of the magnesium compound to butanolwas 1:0.5, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:200 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.004, theratio by weight of the magnesium compound to the porous carrier was 1:2,the ratio by volume of the precipitating agent to the solvent fordissolving the magnesium compound was 1:1, and the ratio by molar of themagnesium compound to titanium tetrachloride was 1:0.2.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1.

Example IV-1-1

Substantially the same as the Example IV-1, except for the followingchanges:

The alcohol was changed to ethanol, the porous carrier was changed tosilica gel (955, from the Grace Company), which has been thermallyactivated by continuously calcinating at 400° C. under a N₂ gasatmosphere for 8 hours.

The nonmetallocene ligand was changed to

the precipitating agent was changed to cyclohexane.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:1, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:240 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.006, theratio by weight of the magnesium compound to the porous carrier was 1:1,the ratio by volume of the precipitating agent to the solvent fordissolving the magnesium compound was 1:0.5, and the ratio by molar ofthe magnesium compound to the chemical treating agent was 1:0.5.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-1.

Example IV-1-2

Substantially the same as the Example IV-1, except for the followingchanges:

The porous carrier was changed to Al₂O₃, which has been thermallyactivated by continuously calcinating at 700° C. under a N₂ gasatmosphere for 6 hours.

The alcohol was changed to propanol, the magnesium compound was changedto magnesium bromide (MgBr₂), the nonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed totoluene, the precipitating agent was changed to cycloheptane, and thechemical treating agent was changed to zirconium tetrachloride (ZrCl₄).

The chemical treating agent was dissolved in 25 ml toluene, and then theresultant solution was dropwise added to the composite carrier over aperiod of 15 minutes. Washing was conducted with toluene for 3 times (25ml each time), and then heated to 120° C. and vacuum dried.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:2, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:100 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.003, theratio by weight of the magnesium compound to the porous carrier was 1:3,the ratio by volume of the precipitating agent to the solvent fordissolving the magnesium compound was 1:2, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:1.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-2.

Example IV-1-3

Substantially the same as the Example IV-1, except for the followingchanges:

The porous carrier was changed to montmorillonite, which has beenthermally activated by continuously calcinating at 400° C. under a N₂gas atmosphere for 8 hours.

The alcohol was changed to iso-octanol, the magnesium compound waschanged to ethoxy magnesium chloride (MgCl(OC₂H₅)), the nonmetalloceneligand was changed to

the solvent for dissolving the magnesium compound was changed to ethylbenzene, the precipitating agent was changed to decane, and the chemicaltreating agent was changed to tetraethyl titanium (Ti(CH₃CH₂)₄).

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:0.25, the ratio of the magnesium compound to the solventfor dissolving the magnesium compound was 1 mol:300 ml, the ratio bymolar of the magnesium compound to the nonmetallocene ligand was1:0.010, the ratio by weight of the magnesium compound to the porouscarrier was 1:0.5, the ratio by volume of the precipitating agent to thesolvent for dissolving the magnesium compound was 3:1, and the ratio bymolar of the magnesium compound to the chemical treating agent was1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-3.

Example IV-1-4

Substantially the same as the Example IV-1, except for the followingchanges:

The porous carrier was changed to polystyrene, which has been thermallyactivated by continuously drying at 100° C. under a N₂ gas atmospherefor 12 hours.

The alcohol was changed to pentanol, the magnesium compound was changedto ethyl magnesium (Mg(C₂H₅)₂), the nonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed to xylene,and the chemical treating agent was changed to triisobutyl chlorotitanium (TiCl(i-C₄H₉)₃).

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:3, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:350 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.001, theratio by weight of the magnesium compound to the porous carrier was1:10, the ratio by volume of the precipitating agent to the solvent fordissolving the magnesium compound was 4:1, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.3.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-4.

Example IV-1-5

Substantially the same as the Example IV-1, except for the followingchanges:

The porous carrier was changed to kieselguhr, which has been thermallyactivated by continuously calcinating at 500° C. under a N₂ gasatmosphere for 8 hours.

The magnesium compound was changed to ethoxy magnesium (Mg(OC₂H₅)₂), thenonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed top-chloro toluene, and the chemical treating agent was changed totetraethoxy titanium (Ti(OCH₃CH₂)₄).

Example IV-1-6

Substantially the same as the Example IV-1, except for the followingchanges:

The magnesium compound was changed to isobutyl magnesium (Mg(i-C₄H₉)₂),the nonmetallocene ligand was changed to

The porous carrier was changed to a mixed oxide of silica and MgO (at aratio by weight of 1:1), which has been thermally activated bycontinuously calcinating at 600° C. under an Ar gas atmosphere for 4hours.

Example IV-2

Anhydrous magnesium chloride was used as the magnesium compound, butanolwas used as the alcohol, tetrahydrofuran was used as the solvent fordissolving the magnesium compound, hexane was used as the precipitatingagent, titanium tetrachloride was used as the chemical treating agent,silica gel (ES757, from the Ineos Company) was used as the porouscarrier, the compound represented by

was used as the nonmetallocene ligand.

The silica gel was thermally activated by continuously calcinating at600° C. under a N₂ atmosphere for 4 hours before use.

2.5 g of anhydrous magnesium chloride as the magnesium compound wasweighted, a predetermined amount of butanol and tetrahydrofuran wereadded thereto, after heated to 60° C. to dissolve same, a predeterminedamount of the nonmetallocene ligand was added thereto and continuouslystirred at 60° C. to completely dissolve same. Then, the thermallyactivated silica gel was added thereto to form a slurry. After stirringfor 2 hours, hexane (as the precipitating agent) was added thereto toprecipitate same. The resultant solid was then filtered, washed by asolvent for washing (which is the same as the precipitating agent) for 2times (by using the same amount as that of the precipitating agent eachtime) and then uniformly heated to 90° C. and vacuum dried, to obtainthe composite carrier.

Then, to the composite carrier, 25 ml hexane was added, and thentriethyl aluminum as the assistant chemical treating agent was dropwiseadded thereto under stirring over a period of 15 minutes. The reactioncontinued under stirring for 1 hour, then filtered, washed with hexanefor 2 times (25 ml each time). Then, 25 ml hexane was added thereto, andthen titanium tetrachloride was dropwise added thereto over a period of15 minutes. The reaction continued at 60° C. for 4 hours, then filtered,washed with hexane for 3 times (25 ml each time), and finally vacuumdried to obtain the supported nonmetallocene catalyst.

In this example, the ratio by molar of the magnesium compound to butanolwas 1:0.5, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:200 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.004, theratio by weight of the magnesium compound to the porous carrier was 1:2,the ratio by volume of the precipitating agent to the solvent fordissolving the magnesium compound was 1:1, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.35,and the ratio by molar of the magnesium compound to titaniumtetrachloride was 1:0.2.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2.

Example IV-2-1

Substantially the same as the Example IV-2, except for the followingchanges:

The alcohol was changed to ethanol, the nonmetallocene ligand waschanged to

the precipitating agent was changed to cyclohexane, the assistantchemical treating agent was changed to methyl aluminoxane.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:1, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:240 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.006, theratio by weight of the magnesium compound to the porous carrier was 1:1,the ratio by volume of the precipitating agent to the solvent fordissolving the magnesium compound was 1:0.5, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.5,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.5.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2-1.

Example IV-2-2

Substantially the same as the Example IV-2, except for the followingchanges:

The alcohol was changed to propanol, the magnesium compound was changedto magnesium bromide (MgBr₂), the nonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed totoluene, the precipitating agent was changed to cycloheptane, theassistant chemical treating agent was changed to isobutyl aluminoxane,and the chemical treating agent was changed to zirconium tetrachloride(ZrCl₄).

The chemical treating agent was dissolved in 25 ml toluene, and then theresultant solution was dropwise added to the composite carrier over aperiod of 15 minutes. Washing was conducted with toluene for 3 times (25ml each time), and then heated to 120° C. and vacuum dried.

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:2, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:100 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.003, theratio by weight of the magnesium compound to the porous carrier was 1:3,the ratio by volume of the precipitating agent to the solvent fordissolving the magnesium compound was 1:2, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.6,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:1.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2-2.

Example IV-2-3

Substantially the same as the Example IV-2, except for the followingchanges:

The alcohol was changed to iso-octanol, the magnesium compound waschanged to ethoxy magnesium chloride (MgCl(OC₂H₅)), the nonmetalloceneligand was changed to

the solvent for dissolving the magnesium compound was changed to ethylbenzene, the precipitating agent was changed to decane, the assistantchemical treating agent was changed to triisobutyl aluminum, and thechemical treating agent was changed to tetraethyl titanium(Ti(CH₃CH₂)₄).

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:0.25, the ratio of the magnesium compound to the solventfor dissolving the magnesium compound was 1 mol:300 ml, the ratio bymolar of the magnesium compound to the nonmetallocene ligand was1:0.010, the ratio by weight of the magnesium compound to the porouscarrier was 1:0.5, the ratio by volume of the precipitating agent to thesolvent for dissolving the magnesium compound was 3:1, the ratio bymolar of the magnesium compound to the assistant chemical treating agentwas 1:1.0, and the ratio by molar of the magnesium compound to thechemical treating agent was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2-3.

Example IV-2-4

Substantially the same as the Example IV-2, except for the followingchanges:

The alcohol was changed to pentanol, the magnesium compound was changedto ethyl magnesium (Mg(C₂H₅)₂), the nonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed to xylene,the assistant chemical treating agent was changed to trimethyl aluminum,and the chemical treating agent was changed to triisobutyl chlorotitanium (TiCl(i-C₄H₉)₃).

In this example, the ratio by molar of the magnesium compound to thealcohol was 1:3, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound was 1 mol:350 ml, the ratio by molarof the magnesium compound to the nonmetallocene ligand was 1:0.001, theratio by weight of the magnesium compound to the porous carrier was1:10, the ratio by volume of the precipitating agent to the solvent fordissolving the magnesium compound was 4:1, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.75,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.3

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2-4.

Example IV-2-5

Substantially the same as the Example IV-2, except for the followingchanges:

The magnesium compound was changed to ethoxy magnesium (Mg(OC₂H₅)₂), thenonmetallocene ligand was changed to

the solvent for dissolving the magnesium compound was changed top-chloro toluene, and the chemical treating agent was changed totetraethoxy titanium (Ti(OCH₃CH₂)₄).

Example IV-2-6

Substantially the same as the Example IV-2, except for the followingchanges:

The magnesium compound was changed to isobutyl magnesium (Mg(i-C₄H₉)₂),the nonmetallocene ligand was changed to

The porous carrier was changed to a mixed oxide of silica and MgO (at aratio by weight of 1:1), which has been thermally activated bycontinuously calcinating at 600° C. under an Ar gas atmosphere for 4hours.

Reference Example IV-1-A

Substantially the same as the Example IV-1, except for the followingchanges:

No nonmetallocene ligand was used.

The thus obtained catalyst was named as CAT-IV-1-A.

Reference Example IV-1-B

Substantially the same as the Example IV-1, except for the followingchanges:

The ratio by molar of the magnesium compound to the nonmetalloceneligand was changed to 1:0.008.

The thus obtained catalyst was named as CAT-IV-1-B.

Reference Example IV-1-C

Substantially the same as the Example IV-1, except for the followingchanges:

The ratio by molar of the magnesium compound to the nonmetalloceneligand was changed to 1:0.002.

The thus obtained catalyst was named as CAT-IV-1-C.

Reference Example IV-1-D

Substantially the same as the Example IV-1, except for the followingchanges:

The composite carrier was not treated by titanium tetrachloride.

The thus obtained catalyst was named as CAT-IV-1-D.

Reference Example IV-1-E

Substantially the same as the Example IV-1, except for the followingchanges:

The composite carrier was not subjected to the treatment of theprecipitating agent, but was obtained by directly vacuum dried at 90° C.

The thus obtained catalyst was named as CAT-IV-1-E.

Example IV-3 Application Example IV

The catalysts CAT-IV-1, CAT-IV-2, CAT-IV-1-1 to CAT-IV-1-4, CAT-IV-2-1to CAT-IV-2-4, CAT-IV-1-A to CAT-IV-1-E were respectively weighted, andused in combination of a co-catalyst (methyl aluminoxane or triethylaluminum), for ethylene homopolymerization/copolymerization and ultrahigh molecular weight polyethylene preparation under the followingconditions according to the following processes respectively.

Homopolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 0.8 MPa, a polymerization temperature of 85°C., a partial pressure of hydrogen gas of 0.2 MPa, a polymerization timeof 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 20 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and then hydrogen gas was supplied thereto till 0.2 MPa,and finally ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 0.8 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table IV-1.

Copolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 0.8 MPa, a polymerization temperature of 85°C., a partial pressure of hydrogen gas of 0.2 MPa, a polymerization timeof 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 20 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto. Hexene-1 (50 g) was added thereto all at once as thecomonomer, and then hydrogen gas was supplied thereto till 0.2 MPa, andfinally ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 0.8 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table IV-1.

Preparation of ultra high molecular weight polyethylene: an autoclavefor polymerization (5 L), a slurry polymerization process, hexane (2.5L) as the solvent, a total polymerization pressure of 0.5 MPa, apolymerization temperature of 70° C., a ratio by molar of theco-catalyst to the active metal in the catalyst of 100, a polymerizationtime of 6 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 20 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and finally ethylene was continuously supplied thereto tokeep the total polymerization pressure constant at 0.5 MPa. Uponcompletion of the polymerization, the inside of the autoclave was ventedto the atmosphere, and the resultant polymer product was discharged fromthe autoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table IV-2.

TABLE IV-1 The results of the olefin polymerization obtained with thesupported nonmetallocene catalysts ratio by molar of co-catalystMolecular Experiment to active Poly activity Bulk density weight No.Catalyst No. Co-catalyst metal type (kgPE/gCat) (g/cm³) distribution 1CAT-IV-1 triethylaluminum 100 homopolymerization 7.2 0.37 3.04 2CAT-IV-1 methylaluminoxane 100 homopolymerization 7.9 0.38 2.59 3CAT-IV-1 triethylaluminum 100 copolymerization 8.6 0.38 3.28 4 CAT-IV-1triethylaluminum 500 copolymerization 9.3 0.38 3.16 5 CAT-IV-1-1triethylaluminum 100 homopolymerization 9.5 0.37 — 6 CAT-IV-1-2triethylaluminum 100 homopolymerization 6.9 0.36 — 7 CAT-IV-1-3triethylaluminum 100 homopolymerization 8.5 0.36 — 8 CAT-IV-1-4triethylaluminum 100 homopolymerization 6.4 0.36 — 9 CAT-IV-2triethylaluminum 100 homopolymerization 8.0 0.37 2.96 10 CAT-IV-2methylaluminoxane 100 homopolymerization 8.9 0.38 2.54 11 CAT-IV-2triethylaluminum 100 copolymerization 9.8 0.38 3.11 12 CAT-IV-2-1triethylaluminum 100 homopolymerization 9.6 0.38 — 13 CAT-IV-2-2triethylaluminum 100 homopolymerization 7.5 0.37 — 14 CAT-IV-2-3triethylaluminum 100 homopolymerization 8.8 0.36 — 15 CAT-IV-2-4triethylaluminum 100 homopolymerization 6.8 0.36 — 16 CAT-IV-1-Atriethylaluminum 100 homopolymerization 5.1 0.31 4.74 17 CAT-IV-1-Btriethylaluminum 100 homopolymerization 8.1 0.37 2.72 18 CAT-IV-1-Ctriethylaluminum 100 homopolymerization 6.7 0.35 3.38 19 CAT-IV-1-Dtriethylaluminum 100 homopolymerization no activity — — 20 CAT-IV-1-Etriethylaluminum 100 homopolymerization 8.2 0.34 2.98

TABLE IV-2 The results of the ultra high molecular weight polyethylenepreparation obtained with the supported nonmetallocene catalysts Polyactivity Bulk Mv Experiment (kgPE/ density (10⁴ No. Catalyst No.Co-catalyst gCat) (g/cm³) g/mol) 1 CAT-IV-1 triethyl 9.8 0.40 430aluminum 2 CAT-IV-1 methyl 9.5 0.42 475 aluminoxane 3 CAT-IV-2 triethyl10.4 0.41 460 aluminum 4 CAT-IV-2 methyl 9.9 0.43 560 aluminoxane 5CAT-IV-1-A triethyl 6.9 0.38 210 aluminum 6 CAT-IV-1-B triethyl 11.20.39 550 aluminum 7 CAT-IV-1-C triethyl 7.6 0.39 370 aluminum 8CAT-IV-1-D triethyl no activity — — aluminum 9 CAT-IV-1-E triethyl 11.10.38 450 aluminum

Upon comparison of the results of the experiment No. 1 and those of theexperiment No. 3, the results of the experiment No. 10 and those of theexperiment No. 11, in the Table IV-1, it is clear that the presentcatalyst shows a significant comonomer effect, i.e. the activity incopolymerization is higher than that in homopolymerization. Further, bythe copolymerization, the bulk density of the polymer can be increased,i.e. the polymer morphology can be improved. However, there is limitedinfluence on the molecular weight distribution of the polymer.

Upon comparison of the results of the experiment No. 1 and those of theexperiment No. 2, the results of the experiment No. 9 and those of theexperiment No. 10, it is clear that the activity of the catalyst forpolymerization in the presence of hydrogen gas can be further increased,the bulk density of the polymer can be further improved, and themolecular weight distribution of the polymer can be further narrowed, ifusing MAO as the co-catalyst.

Upon comparison of the results of the experiment Nos. 1, 17 and 18 inthe Table IV-1, it is clear that by increasing or reducing the ratio bymolar of the nonmetallocene ligand to the magnesium compound, theactivity for ethylene polymerization of the catalyst was increased ordecreased, and the molecular weight distribution of the polymer wassomewhat narrowed or broadened. This effect was further supported by acomparison of the results of the experiment Nos. 16 and 1, i.e. noaddition of the nonmetallocene ligand will lower the activity of thecatalyst and broaden the molecular weight distribution of the polymer.

As can be seen from the Table IV-2, it is possible to prepare an ultrahigh molecular weight polyethylene (with to some degree increased bulkdensity) by using the catalyst according to this invention. Uponcomparison of the results from the experiment No. 1 and those from theexperiment No. 2, the results from the experiment No. 3 and those fromthe experiment No. 4, it is clear that the viscosity averaged molecularweight of the polymer can be increased by using MAO as the co-catalyst.Upon comparison of the results from the experiment No. 1 and those fromthe reference example experiment Nos. 5 to 8 in the Table IV-2, it isclear that the viscosity averaged molecular weight of the polymerincreases or decreases as the amount of the nonmetallocene ligand to beintroduced into the catalyst increases or decreases. This fact indicatesthat the nonmetallocene ligand further shows a function of increasingthe viscosity averaged molecular weight of the polymer.

Upon comparison of the results of the experiment Nos. 1 to 8 and thoseof the experiment Nos. 9 to 15 in the Table IV-1 and the results of theexperiment Nos. 1 to 2 and those of the experiment Nos. 3 to 4 in theTable IV-2, it is clear that the supported nonmetallocene catalystobtained by a process wherein the composite carrier was firstly subjectto the treatment with an assistant chemical treating agent and then tothat with a chemical treating agent shows increased catalyst activityand polymer bulk density, narrowed polymer molecular weight distributionand increased viscosity averaged molecular weight of the ultra highmolecular weight polyethylene, as compared with the supportednonmetallocene catalyst obtained by a process wherein the compositecarrier is subject only to the treatment with a chemical treating agent.

As can be seen from the results of the experiment No. 19 in the TableIV-1 and the results of the experiment No. 8 in the Table IV-2, it isclear that the catalyst containing merely the nonmetallocene ligandshows no polymerization activity, and will be given same after reactingwith the Group IVB metal compound.

Upon comparison of the results of the experiment Nos. 1 and 14 in theTable IV-1 and the results of the experiment Nos. 1 and 9 in the TableIV-2, it is clear that the polymer produced by using the catalystobtained in line with the present process shows a higher polymer bulkdensity than that produced by using a catalyst obtained by a directlydrying process.

It will be apparent to those skilled in the art that variousmodifications and variation can be made in the present invention withoutdeparting from the spirit or scope of the invention. Thus, it isintended that the present invention cover the modifications andvariations of this invention provided they come within the scope of theappended claims and their equivalents.

We claim:
 1. A process for producing a supported nonmetallocene catalystcomprising dissolving at least one magnesium compound and at least onenonmetallocene ligand in the presence of at least one alcohol in atleast one solvent to obtain a magnesium compound solution; drying themagnesium compound solution or introducing into the magnesium compoundsolution at least one precipitating agent to obtain a modified carrier;and treating the modified carrier with at least one chemical treatingagent chosen from the group consisting of Group IVB metal compounds toobtain the supported nonmetallocene catalyst, and wherein the at leastone nonmetallocene ligand is chosen from the group consisting ofcompounds having the following formula,

wherein: q is 0 or 1; d is 1; A is chosen from the group consisting ofan oxygen atom, a sulfur atom, a selenium atom,

—NR²³R²⁴,

—PR²⁸R²⁹, —P(O)R³⁰OR³¹, sulfone groups, sulfoxide groups and —Se(O)R³⁹,wherein N, O, S, Se and P in A each represents a coordination atom; B ischosen from the group consisting of a nitrogen atom, nitrogen-containinggroups, phosphor-containing groups and C₁-C₃₀ hydrocarbylene groups; Dis chosen from the group consisting of a nitrogen atom, an oxygen atom,a sulfur atom, a selenium atom, a phosphor atom, nitrogen-containinggroups, phosphor-containing groups, C₁-C₃₀ hydrocarbylene groups,sulfone groups, sulfoxide groups,

and —P(O)R³²(OR³³), wherein N, O, S, Se and P in D each represents acoordination atom; E is chosen from the group consisting ofnitrogen-containing groups, oxygen-containing groups, sulfur-containinggroups, selenium-containing groups, phosphor-containing groups and cyanogroups, wherein N, O, S, Se and P in E each represents a coordinationatom; G is chosen from the group consisting of C₁-C₃₀ hydrocarbylenegroups, substituted C₁-C₃₀ hydrocarbylene groups and inert functionalgroups; → represents a single bond or a double bond; — represents acovalent bond or an ionic bond; R¹ to R³, R²² to R³³, and R³⁹ are eachindependently chosen from the group consisting of a hydrogen atom,C₁-C₃₀ hydrocarbyl groups, substituted C₁-C₃₀ hydrocarbyl and inertfunctional groups, wherein these groups may be identical to or differentfrom one another, and any adjacent groups may form a bond or a ring withone another.
 2. A process for producing a supported nonmetallocenecatalyst comprising: dissolving at least one magnesium compound and atleast one nonmetallocene ligand in the presence of at least one alcoholin at least one solvent to obtain a magnesium compound solution; mixingat least one carrier chosen from the group consisting of porous carriersand thermally activated porous carriers with the magnesium compoundsolution to obtain a slurry; drying the slurry or introducing into theslurry at least one precipitating agent to obtain a composite carrier;and treating the composite carrier h at least one chemical treatingagent chosen from the group consisting of Group IVB metal compounds toobtain the supported nonmetallocene catalyst, and wherein the at leastone nonmetallocene ligand is chosen from the group consisting ofcompounds having the following formula,

wherein: q is 0 or 1; d is 1; A is chosen from the group consisting ofan oxygen atom, a sulfur atom, a selenium atom,

—NR²³R²⁴,

—PR²⁸R²⁹, —P(O)R³⁰OR³¹, sulfone groups, sulfoxide groups and —Se(O)R³⁹,wherein N, O, S, Se and P in A each represents a coordination atom; B ischosen from the group consisting of a nitrogen atom, nitrogen-containinggroups, phosphor-containing groups and C₁-C₃₀ hydrocarbylene groups; Dis chosen from the group consisting of a nitrogen atom, an oxygen atom,a sulfur atom, a selenium atom, a phosphor atom, nitrogen-containinggroups, phosphor-containing groups, C₁-C₃₀ hydrocarbylene groups,sulfone groups, sulfoxide groups,

and —P(O)R³²(OR³³), wherein N, O, S, Se and P in D each represents acoordination atom; E is chosen from the group consisting ofnitrogen-containing groups, oxygen-containing groups, sulfur-containinggroups, selenium-containing groups, phosphor-containing groups and cyanogroups, wherein N, O, S, Se and P in E each represents a coordinationatom; G is chosen from the group consisting of C₁-C₃₀ hydrocarbylenegroups, substituted C₁-C₃₀ hydrocarbylene groups and inert functionalgroups; → represents a single bond or a double bond; — represents acovalent bond or an ionic bond; R¹ to R³, R²² to R³³, and R³⁹ are eachindependently chosen from the group consisting of a hydrogen atom,C₁-C₃₀ hydrocarbyl groups, substituted C₁-C₃₀ hydrocarbyl and inertfunctional groups, wherein these groups may be identical to or differentfrom one another, and any adjacent groups may form a bond or a ring withone another.
 3. The process according to claim 1 or 2, furthercomprising pre-treating the composite carrier or the modified carrierwith at least one assistant chemical treating agent chosen from thegroup consisting of aluminoxanes and alkylaluminums before treating thecomposite carrier or the modified carrier with the at least one chemicaltreating agent.
 4. The process according to claim 2, wherein the atleast one carrier is chosen from the group consisting of olefinhomopolymers or copolymers, vinyl alcohol homopolymers or copolymers,cyclodextrins, polyesters or co-polyesters, polyamides or co-polyamides,vinyl chloride homopolymers or copolymers, acrylic ester homopolymers orcopolymers, methacrylic ester homopolymers or copolymers, styrenehomopolymers or copolymers, partly crosslinked products of thesehomopolymers or copolymers, refractory oxides or refractory compositeoxides of a Group IIA, IIIA, IVA or IVB metal, clay, molecular sieve,mica, montmorillonite, bentonite and kieselguhr.
 5. The processaccording to claim 4, wherein the at least one carrier is chosen fromthe group consisting of partly crosslinked styrene polymers, silica,alumina, magnesia, silica-alumina, magnesia-alumina, titanium oxide,molecular sieve and montmorillonite.
 6. The process according to claim 1or 2, wherein the at least one magnesium compound is chosen from thegroup consisting of magnesium halides, alkoxy magnesium halides, alkoxymagnesiums, alkyl magnesiums, alkyl magnesium halides and alkyl alkoxymagnesiums.
 7. The process according to claim 6, wherein the at leastone magnesium compound is chosen from the group consisting of magnesiumhalides.
 8. The process according to claim 1 or 2, wherein the at leastone solvent is chosen from the group consisting of C₆₋₁₂ aromatichydrocarbons, halogenated C₆₋₁₂ aromatic hydrocarbons, esters andethers, and the at least one alcohol is chosen from the group consistingof aliphatic alcohols, aromatic alcohols and alicyclic alcoholsoptionally substituted by at least one substituent chosen from the groupconsisting of halogen atoms and C₁₋₆ alkoxy groups.
 9. The processaccording to claim 8, wherein the at least one solvent is chosen fromthe group consisting of C₆₋₁₂ aromatic hydrocarbons and tetrahydrofuran,and the at least one alcohol is chosen from the group consisting ofaliphatic alcohols.
 10. The process according to claim 1 or 2, whereinthe at least one nonmetallocene ligand is chosen from the groupconsisting of compound (A) and compound (B),

wherein, F is chosen from the group consisting of a nitrogen atom,nitrogen-containing groups, oxygen-containing groups, sulfur-containinggroups, selenium-containing groups and phosphor-containing groups,wherein N, O, S, Se and P in F each represents a coordination atom. 11.The process according to claim 10, wherein the at least onenonmetallocene ligand is chosen from the group consisting of compound(A-1), compound (A-2), compound (A-3), compound (A-4), compound (B-1),compound (B-2), compound (B-3), and compound (B-4),

wherein, Y is chosen from the group consisting of nitrogen-containinggroups, oxygen-containing groups, sulfur-containing groups,selenium-containing groups and phosphor-containing groups, wherein N, O,S, Se and P in Y each represents a coordination atom; Z is chosen fromthe group consisting of nitrogen-containing groups, oxygen-containinggroups, sulfur-containing groups, selenium-containing groups,phosphor-containing groups and cyano groups, wherein N, O, S, Se and Pin Z each represents a coordination atom; R⁴, and R⁶ to R²¹ are eachindependently chosen from the group consisting of a hydrogen atom,C₁-C₃₀ hydrocarbyl groups, substituted C₁-C₃₀ hydrocarbyl groups andinert functional groups, wherein these groups may be identical to ordifferent from one another, and any adjacent groups may form a bond or aring with one another; and R⁵ is chosen from the group consisting of alone pair electron on a nitrogen atom, a hydrogen atom, C₁-C₃₀hydrocarbyl groups, substituted C₁-C₃₀ hydrocarbyl groups,oxygen-containing groups, sulfur-containing groups, nitrogen-containinggroups, selenium-containing groups, and phosphor-containing groups, withthe proviso that when R⁵ is chosen from the group consisting ofoxygen-containing groups, sulfur-containing groups, nitrogen-containinggroups, selenium-containing groups and phosphor-containing groups, N, O,S, P and Se in the R⁵ each can act as a coordination atom.
 12. Theprocess according to claim 11, wherein, the halogen atom is chosen fromthe group consisting of F, Cl, Br and I. the nitrogen-containing groupsare chosen from the group consisting of

—NR²³R²⁴, and -T-NR²³R²⁴, the phosphor-containing groups are chosen fromthe group consisting of

—PR²⁸R²⁹, —P(O)R³⁰R³¹ and —P(O)R³²(OR³³), the oxygen-containing groupsare chosen from the group consisting of hydroxy, —OR³⁴ and -T-OR³⁴, thesulfur-containing groups are chosen from the group consisting of —SR³⁵,-T-SR³⁵, —S(O)R³⁶ and -T-SO₂R³⁷, the selenium-containing groups arechosen from the group consisting of —SeR³⁸, -T-SeR³⁸, —Se(O)R³⁹ and-T-Se(O)R³⁹, the group T is chosen from the group consisting of C₁-C₃₀hydrocarbylene groups, substituted C₁-C₃₀ hydrocarbylene groups andinert functional groups, R³⁷ is chosen from the group consisting of ahydrogen atom, C₁-C₃₀ hydrocarbyl groups, substituted C₁-C₃₀ hydrocarbylgroups and inert functional groups, the C₁-C₃₀ hydrocarbyl groups arechosen from the group consisting of C₁-C₃₀ alkyl groups, C₇-C₅₀alkylaryl groups, C₇-C₅₀ aralkyl groups, C₃-C₃₀ cyclic alkyl groups,C₂-C₃₀ alkenyl groups, C₂-C₃₀ alkynyl groups, C₆-C₃₀ aryl groups, C₈-C₃₀fused-ring groups and C₄-C₃₀ heterocycle groups, wherein the C₄-C₃₀heterocycle group contains 1 to 3 hetero atom(s) chosen from the groupconsisting of a nitrogen atom, an oxygen atom and a sulfur atom, thesubstituted C₁-C₃₀ hydrocarbyl groups are chosen from the groupconsisting of C₁-C₃₀ hydrocarbyl groups having at least one substituentchosen from the group consisting of halogen atoms and C₁-C₃₀ alkylgroups, the inert functional groups are chosen from the group consistingof halogen atoms, oxygen-containing groups, nitrogen-containing groups,silicon-containing groups, germanium-containing groups,sulfur-containing groups, tin-containing groups, C₁-C₁₀ ester groups andnitro groups, the silicon-containing groups are chosen from the groupconsisting of —siR⁴²R⁴³R⁴⁴, and -T-SiR⁴⁵, the germanium-containinggroups are chosen from the group consisting of —GeR⁴⁶R⁴⁷R⁴⁸ and-T-GeR⁴⁹, the tin-containing groups are chosen from the group consistingof —SnR⁵⁰R⁵¹R⁵², -T-SnR⁵³ and -T-Sn(O)R⁵⁴, R³⁴ to R³⁶, R³⁸ and R⁴² toR⁵⁴ are each independently chosen from the group consisting of ahydrogen atom, C₁-C₃₀ hydrocarbyl groups, substituted C₁-C₃₀ hydrocarbylgroups and inert functional groups, wherein these groups may beidentical to or different from one another, and any adjacent groups mayform a bond or a ring with one another.
 13. The process according toclaim 1 or 2, wherein the at least one nonmetallocene ligand is chosenfrom the group consisting of:


14. The process according to claim 2, wherein molar ratio of the atleast one magnesium compound (based on Mg) to the at least onenonmetallocene ligand is 1:0.0001-1, ratio of the at least one magnesiumcompound to the at least one solvent is 1 mol:75-400 ml, molar ratio ofthe at least one magnesium compound (based on Mg) to the at least onealcohol is 1:0.02-4.00, weight ratio of the at least one magnesiumcompound (on a solid basis) to the at least one carrier is 1:0.1-20,volume ratio of the at least one precipitating agent to the at least onesolvent is 1:0.2-5, and molar ratio of the at least one magnesiumcompound (based on Mg) to the at least one chemical treating agent(based on the Group IVB metal) is 1:0.01-1.
 15. The process according toclaim 1 or 2, wherein the at least one precipitating agent is chosenfrom the group consisting of alkanes, cyclic alkanes, halogenatedalkanes and halogenated cyclic alkanes.
 16. The process according toclaim 15, wherein the at least one precipitating agent is chosen fromthe group consisting of hexane, heptane, decane and cyclohexane.
 17. Theprocess according to claim 1 or 2, wherein the Group IVB metal compoundsare chosen from the group consisting of Group IVB metal halides, GroupIVB metal alkylates, Group IVB metal alkoxylates, Group IVB metal alkylhalides, and Group IVB metal alkoxy halides.
 18. The process accordingto claim 17, wherein the Group IVB metal compounds are chosen from thegroup consisting of Group IVB metal halides.
 19. The process accordingto claim 3, wherein the aluminoxanes are chosen from the groupconsisting of methyl aluminoxane, ethyl aluminoxane, isobutylaluminoxane and n-butyl aluminoxane, and the alkylaluminums are chosenfrom the group consisting of trimethyl aluminum, triethyl aluminum,tripropyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum,triisoamyl aluminum, tri-n-amyl aluminum, trihexyl aluminum,tri-iso-hexyl aluminum, diethyl methyl aluminum and ethyl dimethylaluminum.
 20. The process according to claim 3, wherein molar ratio ofthe at least one magnesium compound (based on Mg) to the at least oneassistant chemical treating agent (based on Al) is 1:0-1.0.
 21. Asupported nonmetallocene catalyst, produced according to the process ofclaim 1 or
 2. 22. An olefin homopolymerization/copolymerization processcomprising polymerizing at least one olefin in the presence of thesupported nonmetallocene catalyst according to claim 21 with at leastone co-catalyst chosen from the group consisting of aluminoxane, analkylaluminum, a halogenated alkyl aluminum, a fluoroborane, analkylboron and an alkylboron ammonium salts.